Use of polymeric reaction product

ABSTRACT

A reaction product (A) which can be prepared by reaction, under free radical conditions, of at least one monomer (a) capable of free radical reaction, in the presence of at least one free radical initiator and of a radical of the formula (III)  
                 
 
     where R 1  to R 3 , in each case independently of one another, are hydrogen, methyl or a radical-stabilizing and/or bulky group selected from an unsubstituted or substituted, linear or branched alkyl of two or more carbon atoms, cycloalkyl, alcohol, ether, polyether, amine, aralkyl radical, a substituted or unsubstituted aromatic, heterocyclic or olefinic hydrocarbon, a halogen atom, a substituted or unsubstituted, linear or branched alkenyl or alkynyl group, —C(O)R 5 , —C(O)OR 5 , —CR 5 R 6 —O—R 7 , —O—C(O)R 5 , —CN, —O—CN, —S—CN, —O—C═NR 5 , —S—C═NR 5 , —O—CR 5 R 6 —CR 7 R 8 NR 9 R 10 , —N═C═O, —C═NR 5 , —CR 5 R 6 -Hal, —C(S)R 5 , —CR 5 R 6 —P(O)R 7 R 8 , —CR 5 R 6 —PR 7 R 8 , —CR 5 R 6 —NR 7 R 8 , —CR 5 R 6 (OR 7 )(OR 8 ), —CR 5 R 6 (OR 7 )(NR 8 ), —CR 5 R 6 (NR 7 )(NR 8 ), an anhydride, acetal or ketal group, —SO 2 R 5 , an amidine group, —NR 5 C(S)NR 6 , —NR 5 C(S)—OR 6 , —N═C═S, —NO 2 , —C═N—OH, —N(R 5 )═NR 6 , —PR 5 R 6 R 7 , —OSiR 5 R 6 R 7  or —SiR 5 R 6 R 7 , where R 5  to R 10 , independently of one another in each case, are defined in the same way as R 1  to R 5 , or two of the radicals R 1  to R 4  form a C 4 - to C 7 -ring which in turn may be substituted or unsubstituted and, if required, may contain one or more heteroatoms, with the proviso that at least two of the radicals R 1  to R 3  are a radical-stabilizing and/or bulky group as defined above, has various uses.

[0001] The present invention relates to various uses of a reactionproduct (A) which was prepared by reaction, under free radicalconditions, of at least one monomer (a), capable of free radicalreaction, in the presence of at least one free radical initiator and ofa radical of the formula (III), as defined below.

[0002] The technical field of the present invention is the use ofreaction products or polymers which were prepared by free radicalpolymerization in many applications in various technical fields, such asinkjet inks, cosmetics, coating materials and engineering materials.

[0003] The reaction products (A) or polymers (B) used within the scopeof the present invention are known per se or form the subject of aparallel application of the Applicant.

[0004] In this context, reference may be made to DE 198 58 708.2 and theprior art cited therein. The preparation of the polymers used accordingto the invention has moreover been the subject of numerous scientificinvestigations.

[0005] A free radical chain polymerization or copolymerization with anω-unsaturated oligo(methyl methacrylate) with ethyl acrylate, styrene,methyl methacrylate, acrylonitrile and vinyl acetate as copolymers isdescribed in a scientific article in J. Macromol. Sci. Chem. A 23 (7)(1986), 839-852.

[0006] Furthermore, free radical chain polymerizations andcopolymerizations using 1,2-(trimethylsilyloxy)tetraphenylethane aredescribed in Macromol. Chem. Phys. 201 (2000), 74-83, methylmethacrylate, styrene, phenyl acetate, butyl acrylate and glycidylmethacrylate being used as monomers there.

[0007] An overview of free radical chain polymerizations using inparticular tetraphenylethane (derivatives) is given by Otsu andMatsumoto in Advances in Polymer Science 136, 75-137, and in PolymerBulletin 16 (1986), 95-102.

[0008] Furthermore, Harwood et al. in Macromol. Symp. 111 (1996), 25-35report on NMR investigations into random, block and graft copolymersusing NMR-sensitive initiators and macroinitiators. Inter alia, thereaction of a methyl methacrylate/stilbene mixture and the properties ofthe polymer resulting therefrom are described there.

[0009] The abovementioned scientific papers are concerned exclusivelywith the reaction mechanism on which free radical chain polymerizationis based or relate to investigations into the structure of the resultingproducts. Possible uses of the reaction products or polymers discussedtherein are not mentioned.

[0010] It is an object of the present invention to demonstrate thenumerous potential uses of such specific reaction products or polymersprepared by free radical chain polymerization. The reaction products andpolymers described herein are of considerable interest since the chosenmethod of preparation makes it possible to establish the properties ofthese products in a specific manner with regard to the wide range ofpotential uses, in particular by the preparation of block structures bymeans of free radical polymerization.

[0011] In the context of the present invention, a block copolymer isunderstood as meaning a polymer which has at least two polymer blockscharacterized by different monomer compositions. In the context of thepresent invention, different monomer compositions is understood asmeaning that at least two regions of the block copolymer have differentmonomer compositions. In the context of the present invention, it ispossible for the transition between two blocks to be continuous, i.e.,for there to exist between two blocks a zone which has a random orregular sequence of the monomers constituting the blocks. In the contextof the present invention, however, it is also envisaged that thetransition between two blocks is essentially discontinuous. Anessentially discontinuous transition is understood as meaning atransition zone which has a substantially shorter length than at leastone of the blocks separated by the transition zone. It is possible for ablock to be based only on one type of monomer. However, it is alsoenvisaged that a block is composed of two or more monomers. In apreferred embodiment of the present invention, the chain length of sucha transition zone is less than {fraction (1/10)}, preferably less than{fraction (1/20)}, of the block length of at least one of the blocksseparated by the transition zone.

[0012] In the context of the present invention different monomercompositions is furthermore understood as meaning that the monomersconstituting the respective block differ in at least one feature, forexample in their linkage to one another, in their conformation or intheir constitution. If, as described above, a block is composed of morethan one type of monomer, in the present context different blocks of theblock copolymer can, for example, also differ by having differentconcentrations of the monomers constituting a block in each case. In thecontext of the present invention, block copolymers preferably used arethose which have at least two blocks whose monomer compositions differat least in the constitution of the monomers.

[0013] We have found that the abovementioned and further objects areachieved by the use of a reaction product (A) which can be prepared bymeans of a process comprising the following stage (i):

[0014] (i) Reaction, under free radical conditions, of a reactionmixture comprising at least one monomer (a), capable of free radicalreaction, in the presence of at least one radical of the formula (III)

[0015] where R₁ to R₃, in each case independently of one another, arehydrogen, methyl or a radical-stabilizing and/or bulky group selectedfrom an unsubstituted or substituted, linear or branched alkyl of two ormore carbon atoms, cycloalkyl, alcohol, ether, polyether, amine, aralkylradical, a substituted or unsubstituted aromatic, heterocyclic orolefinic hydrocarbon, a halogen atom (Hal), a substituted orunsubstituted, linear or branched alkenyl or alkynyl group, —C(O)R₅,—C(O)OR₅, —CR₅R₆—O—R₇, —O—C(O)R₅, —CN, —O—CN, —S—CN, —O—C═NR₅, —S—C═NR₅,—O—CR₅R₆—CR₇R₈NR₉R₁₀, —N═C═O, —C—NR₅, —CR₅R₆-Hal, —C(S)R₅,—CR₅R₆—P(O)R₇R₈, —CR₅R₆—PR₇R₈, —CR₅R₆—NR₇R₈, —CR₅R₆(OR₇)(OR₈),—CR₅R₆(OR₇)(NR₈), —CR₅R₆(NR₇)(NR₈), an anhydride, acetal or ketal group,—SO₂R₅, an amidine group, —NR₅C(S)NR₆, —NR₅C(S)—OR₆, —N═C═S, —NO₂,—C═N—OH, —N(R₅)═NR₆, —PR₅R₆R₇, —OSiR₅R₆R₇ or —SiR₅R₆R₇, where R₅ to R₁₀,independently of one another in each case, are defined in the same wayas R₁ to R₄, or two of the radicals R₁ to R₄ form a C₄- to C₇-ring whichin turn may be substituted or unsubstituted and, if required, maycontain one or more heteroatoms,

[0016] with the proviso that

[0017] at least two of the radicals R₁ to R₃ are a radical-stabilizingand/or bulky group as defined above,

[0018] as a component in coating materials,

[0019] in finishes and coating materials,

[0020] as a component in toners,

[0021] as a component in cosmetics,

[0022] as a component in resin material,

[0023] as a component in retention aids for papermaking,

[0024] as a component in solubilizers in pharmaceutical and cosmeticformulations,

[0025] as incrustation inhibitors and/or soil-release polymers indetergents,

[0026] as a component in filtration assistants and for protecting andclarifying beverages,

[0027] as a component in disinfectants,

[0028] as a component in elastomeric binders,

[0029] in printing plates,

[0030] as a dispersant, preferably in inkjet pigment formulations,

[0031] as an assistant in a tablet matrix,

[0032] as an assistant in the plasticizing of concrete,

[0033] as biodegradable polymers for, for example, materials forimplants, surgical suture materials and garbage bags,

[0034] as a component in wallpaper adhesive,

[0035] as a component of plastics used in automotive construction, inthe household sector, for leisure articles, in the production of roadsigns, window profiles, lamp covers, garden furniture, boats,surfboards, toys, in the packaging sector, in the production of massageapparatuses and housings therefor, in the production of medicalequipment, in the production of equipment for information processing andtransmission, in the production of extensive wall elements, in transportcontainers, in

[0036] housings for electrical equipment, in moldings for theconstruction sector or in grating covers, and

[0037] the use of a polymer (B) which can be prepared by a processcomprising the stage (ii):

[0038] (ii) Reaction of the reaction product (A) obtained in stage (i),under free radical conditions, in the presence of at least one monomer(b) capable of free radical homopolymerization or copolymerization,

[0039] as a component in coating materials,

[0040] in finishes and coating materials,

[0041] as a component in toners,

[0042] as a component in cosmetics,

[0043] as a component in resin material,

[0044] as a component in retention aids for papermaking,

[0045] as a component in solubilizers in pharmaceutical and cosmeticformulations,

[0046] as a component in incrustation inhibitors and/or soil-releasepolymers in detergents,

[0047] as a component in filtration assistants and for protecting andclarifying beverages,

[0048] as a component in disinfectants,

[0049] as a component in elastomeric binders,

[0050] in printing plates,

[0051] as a dispersant, preferably in inkjet pigment formulations,

[0052] as an assistant in a tablet matrix,

[0053] as an assistant in the plasticizing of concrete,

[0054] as biodegradable polymers for, for example, materials forimplants, surgical suture materials and garbage bags,

[0055] as a component in wallpaper adhesive,

[0056] as a component of plastics used in automotive construction, inthe household sector, for leisure articles, in the production of roadsigns, window profiles, lamp covers, garden furniture, boats,surfboards, toys, in the packaging sector, in the production of massageapparatuses and housings therefor, in the production of medicalequipment, in the production of equipment for information processing andtransmission, in the production of extensive wall elements, in transportcontainers, in housings for electrical equipment, in moldings for theconstruction sector or in grating covers.

[0057] Preferably, the radical of the formula (III) is derived from atleast one compound of the formula (I)

[0058] where R₁ to R₄, in each case independently of one another, arehydrogen, methyl or a radical-stabilizing and/or bulky group selectedfrom an unsubstituted or substituted, linear or branched alkyl of two ormore carbon atoms, cycloalkyl, alcohol, ether, polyether, amine, aralkylradical, a substituted or unsubstituted aromatic, heterocyclic orolefinic hydrocarbon, a halogen atom, a substituted or unsubstituted,linear or branched alkenyl or alkynyl group, —C(O)R₅, —C(O)OR₅,—CR₅R₆—O—R₇, —O—C(O)R₅, —CN, —O—CN, —S—CN, —O—C═NR₅, —S—C═NR₅,—O—CR₅R₆—CR₇R₈NR₉R₁₀, —N═C═O, —C═NR₅, —CR₅R₆-Hal, —C(S)R₅,—CR₅R₆—P(O)R₇R₈, —CR₅R₆—PR₇R₈, —CR₅R₆—NR₇R₈, —CR₅R₆(OR₇)(OR₈),—CR₅R₆(OR₇)(NR₈), —CR₅R₆(NR₇)(NR₈), an anhydride, acetal or ketal group,—SO₂R₅, an amidine group, —NR₅C(S)NR₆, —NR₅C(S)—OR₆, —N═C═S, —NO₂,—C═N—OH, —N(R₅)═NR₆, —PR₅R₆R₇, —OSiR₅R₆R₇ or —SiR₅R₆R₇, where R₅ to R₁₀,independently of one another in each case, are defined in the same wayas R₁ to R₄, or two of the radicals R₁ to R₄ form a C₄- to C₇-ring whichin turn may be substituted or unsubstituted,

[0059] with the proviso that

[0060] at least two of the radicals R₁ to R₄ are a radical-stabilizingand/or bulky group, as defined above, or diphenylethylene,dinaphthylethylene, 4,4′-vinylidenebis(N,N′-dimethylaniline),4,4′-vinylidenebis(aminobenzene) or cis- or trans-stilbene,

[0061] and/or

[0062] from at least one compound of the formula (II)

[0063] where R₁ to R₄ and R₁₁ and R₁₂, in each case independently of oneanother, are hydrogen, methyl or a radical-stabilizing and/or bulkygroup selected from an unsubstituted or substituted, linear or branchedalkyl of two or more carbon atoms, cycloalkyl, alcohol, ether,polyether, amine, aralkyl radical, a substituted or unsubstitutedaromatic, heterocyclic or olefinic hydrocarbon, a halogen atom, asubstituted or unsubstituted, linear or branched alkenyl or alkynylgroup, —C(O)R₅, —C(O)OR₅, —CR₅R₆—O—R₇, —O—C(O)R₅, —CN, —O—CN, —S—CN,—O—C═NR₅, —S—C═NR₅, —O—CR₅R₆—CR₇R₈NR₉R₁₀, —N═C═O, —C═NR₅, —CR₅R₆-Hal,—C(S)R₅, —CR₅R₆—P(O)R₇R₈, —CR₅R₆—PR₇R₈, —CR₅R₆—NR₇R₈, —CR₅R₆(OR₇)(OR₈),—CR₅R₆(OR₇)(NR₈), —CR₅R₆(NR₇)(NR₈), an anhydride, acetal or ketal group,—SO₂R₅, an amidine group, —NR₅C(S)NR₆, —NR₅C(S)—OR₆, —N═C═S, —NO₂,—C═N—OH, —N(R₅)═NR₆, —PR₅R₆R₇, —OSiR₅R₆R₇ or —SiR₅R₆R₇, where R₅ to R₁₀,independently of one another in each case, are defined in the same wayas R₁ to R₄, or two of the radicals R₁ to R₄ form a C₄- to C₇-ring whichin turn may be substituted or unsubstituted and, if required, maycontain one or more heteroatoms,

[0064] with the proviso that

[0065] at least two of R₁ to R₄ are a radical-stabilizing and/or bulkygroup, as defined above.

[0066] In the preparation of the reaction product (A) used according tothe invention and/or of the polymer (B), all monomers capable of freeradical reaction can be used as monomer (a).

[0067] It is of course also possible to use mixtures of differentmonomers as monomers (a) in the context of the present invention.

[0068] According to the abovementioned process, it is also possible topolymerize mixtures of at least one hydrophilic monomer and at least onehydrophobic monomer.

[0069] Specific examples of monomers (a) are:

[0070] Dienes, such as butadiene, isoprene, myrcene, pentadienes, andfurthermore C₁- to C₂₀-alkyl and hydroxyalkyl esters ofmonoethylenically unsaturated C₃- to C₁₀-monocarboxylic acids or C₄- toC₈-dicarboxylic acids, for example methyl methacrylate, ethylmethacrylate, propyl methacrylate (all isomers), butyl methacrylate (allisomers), 2-ethylhexyl methacrylate, isobornyl methacrylate, methylacrylate, ethyl acrylate, propyl acrylate (all isomers), butyl acrylate(all isomers), 2-ethylhexyl acrylate, isobornyl acrylate, benzylacrylate, phenyl acrylate, stearyl acrylate, diethyl maleate,hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate,furthermore (meth)acrylates of alkoxylated C₁- to C₁₈-alcohols whichhave been reacted with from 2 to 50 mol of ethylene oxide, propyleneoxide, butylene oxide and mixtures thereof; benzyl methacrylate, phenylmethacrylate, stearyl methacrylate, methacrylonitrile, styrene,α-methylstyrene, acrylonitrile, functionalized methacrylates; acrylatesand styrenes selected from glycidyl methacrylate, 2-hydroxyethylmethacrylate, hydroxypropyl methacrylate (all isomers), hydroxybutylmethacrylate (all isomers), cyclohexyl methacrylate, cyclohexylacrylate, hexyl methacrylate and hexyl acrylate (in each case allisomers), diethylaminoethyl methacrylate, triethylene glycolmethacrylate, itaconic anhydride, itaconic acid, glycidyl acrylate,2-hydroxyethyl methacrylate, diethylaminoethyl acrylate, triethyleneglycol acrylate, methacrylamide, N-tert-butylmethacrylamide,N-n-butylmethacrylamide, N-methylolmethacrylamide,N-ethylolmethacrylamide, N-tert-butylacrylamide, N-butylacrylamide,N-methylolacrylamide, N-ethylolacrylamide, vinylbenzoic acid (allisomers), diethylaminostyrene (all isomers), α-methylvinylbenzoic acid(all isomers), diethylamino-α-methylstyrene (all isomers),p-methylstyrene, p-vinylbenzenesulfonic acid, trimethoxysilylpropylmethacrylate, triethoxysilylpropyl methacrylate, tributoxysilylpropylmethacrylate, triethoxy-methylsilyipropyl methacrylate,dibutoxymethylsilylpropyl methacrylate, diisopropoxynethylsilylpropylmethacrylate, dimethoxysilylpropyl methacrylate, diethoxysilylpropylmethacrylate, dibutoxysilylpropyl methacrylate, diisopropoxysilylpropylmethacrylate, trimethoxysilylpropyl acrylate, triethoxysilylpropylacrylate, tributoxysilylpropyl acrylate, dimethoxymethylsilylpropylacrylate, diethoxymethylsilylpropyl acrylate, dibutoxymethylsilylpropylacrylate, diisopropoxymethylsilylpropyl acrylate, dimethoxysilylpropylacrylate, diethoxysilylpropyl acrylate, dibutoxysilylpropyl acrylate,diisopropoxysilylpropyl acrylate, vinyl acetate and vinyl butyrate,vinyl chloride, vinyl fluoride, vinyl bromide, vinyl alcohol, vinylethers of C₁- to C₁₈-alcohols, vinyl ethers of alkoxylated C₁- toC₁₈-alcohols and vinyl ethers of polyalkylene oxides, such aspolyethylene oxide, polypropylene oxide or polybutylene oxide,monoethylenically unsaturated C₃- to C₁₀-monocarboxylic acids, theiralkali metal salts and/or ammonium salts, for example acrylic acid,methacrylic acid, dimethylacrylic acid, ethylacrylic acid, allylacelicacid or vinylacetic acid, furthermore monoethylenically unsaturated C₄-to C₈-dicarboxylic acids, their monoesters, anhydrides, alkali metalsalts and/or ammonium salts, for example maleic acid, fumaric acid,itaconic acid, mesaconic acid, methylenemalonic acid, citraconic acid,maleic anhydride, itaconic anhydride or methylmalonic anhydride;furthermore monoethylenically unsaturated monomers containing sulfogroups and their salts, for example their alkali metal or ammoniumsalts, for example allylsulfonic acid, styrenesulfonic acid,2-acrylamido-2-methylpropanesulfonic acid (AMPS), methallylsulfonicacid, vinylsulfonic acid, 3-sulfopropyl acrylate or 3-sulfopropylmethacrylate, furthermore monoethylenically unsaturated monomerscontaining phosphonic acid groups or their salts, for example theiralkali metal or ammonium salts, for example vinylphosphonic acid,allylphosphonic acid or acrylamidoethylpropanephosphonic acid,furthermore amides and N-substituted amides of monoethylenicallyunsaturated C₃- to C₁₀-monocarboxylic acids or C₄- to C₈-dicarboxylicacids, for example acrylamide, N-alkylacrylamides orN,N-dialkylacrylamides, each having 1 to 18 carbon atoms in the alkylgroup, such as N-methylacrylamide, N,N-dimethylacrylamide,N-tert-butylacrylamide or N-octadecylacrylamide,N-monomethylhexylmaleamide, N-monodecylmaleamide,diethylaminopropylmethacrylamide or acrylamidoglycollic acid;furthermore alkylaminoalkyl (meth)acrylates, for exampledimethylaminoethyl acrylate, dimethylaminoethyl methacrylate,ethylaminoethyl acrylate, diethylaminoethyl methacrylate,dimethylaminopropyl acrylate or dimethylaminopropyl methacrylate;furthermore vinyl esters, such as vinyl formate, vinyl acetate or vinylpropionate, where these may also be present in hydrolyzed form after thepolymerization; furthermore N-vinyl compounds, for exampleN-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide,N-vinyl-N-methylformamide, 1-vinyl-imidazole or1-vinyl-2-methylimidazole; furthermore vinyl ethers of C₁- toC₁₈-alcohols, vinyl ethers of alkoxylated C₁- to C₁₈-alcohols and vinylethers of polyalkylene oxides, such as polyethylene oxide, polypropyleneoxide or polybutylene oxide, styrene or its derivatives such asα-methylstyrene, indene, dicyclopentadiene, monomers which carry aminoor imino groups, such as dimethylaminoethyl methacrylate,diethylaminoethyl acrylate, diethylaminopropyl methacrylamide orallylamine, monomers which carry quaternary ammonium groups, for examplepresent as salts, as obtained by reacting basic amino functions withacids, such as hydrochloric acid, sulfuric acid, nitric acid, formicacid or acetic acid, or in quaternized form (examples of suitablequaternizing agents are dimethyl sulfate, diethyl sulfate, methylchloride, ethyl chloride or benzyl chloride), e.g. dimethylaminoethylacrylate hydrochloride, diallyldimethylammonium chloride,dimethylaminoethyl acrylate methylchloride,dimethylaminoethylaminopropylmethacrylamide methosulfate,vinylpyridinium salts or 1-vinylimidazolium salts; monomers in which theamino groups and/or ammonium groups are liberated only after thepolymerization and subsequent hydrolysis, for example N-vinylformamideor N-vinylacetamide, and mixtures of two or more of the abovementionedmonomers.

[0071] Styrenes, acrylonitrile, (meth)acrylates or their free acid,dienes or N-vinyl compounds, preferably the members of this group whichhave been mentioned above, or mixtures of two or more thereof, ifrequired with at least one further monomer (a) capable of free radicalhomopolymerization or copolymerization, are preferably used as a firstmonomer (a).

[0072] According to the invention, a compound of the formula (I)

[0073] or of the formula (II)

[0074] is furthermore used in the preparation of the reaction product(A), in order to obtain the radical of the formula (III).

[0075] Here too, in principle all compounds of the abovementionedformulae can be used according to the invention, provided that theycorrespond to the above definition or the definition given in theclaims.

[0076] It is particularly important that at least two of the radicals R₁to R₄ or R₁ to R₃ in formula (III) are a radical-stabilizing and/orbulky group. The term bulky group as used in the context of the presentinvention means that it is a group whose dimensions in each case in thenovel reaction under free radical conditions are greater than or equalto the dimensions of an isopropyl radical. The term radical-stabilizinggroup used according to the invention denotes groups of the type definedin claim 1, whose electron structure permits stabilization of radicals.

[0077] Specific examples are the following groups of the abovementionedtype: branched alkyl groups of three or more carbon atoms, in particularisopropyl and tert-butyl; cycloalkyl groups, for example unsubstitutedor substituted cyclopentyl or cyclohexyl; alcohol groups, for exampleradicals of branched alcohols, such as isopropoxy or tert-butoxy;aralkyl radicals; substituted or unsubstituted aromatic or heterocyclichydrocarbons, such as phenyl or pyridyl; halogen; cyano; nitro; estergroups of the structure —C(O)OR₅, where the radical R₅ may be, forexample, linear or branched, unsubstituted or substituted alkyl, aralkylor an aromatic or heteroaromatic group.

[0078] Other preferred compounds of the formula (I) are those whichhave, as radical-stabilizing groups, the following combination ofgroups:

[0079] at least one substituted or unsubstituted phenyl or C(O)R₅;

[0080] at least one substituted or unsubstituted phenyl and CN;

[0081] at least one substituted or unsubstituted phenyl and C(O)OR₅;

[0082] independently of one another, at least two substituted orunsubstituted phenyl groups,

[0083] independently of one another, at least two C(O)OR₅; and

[0084] independently of one another, at least two CN.

[0085] In particular.

[0086] 1,1,4,4-tetraphenyl 1,3-butadiene

[0087] 1,4-bis(2-methylstyryl)benzene

[0088] 1,2,3,4,5-pentaphenyl-1,3 -cyclopentadiene

[0089] 1,2,3,4-tetraphenyl-1,3-cyclopentadiene

[0090] acenaphthylene

[0091] cis- and trans-alpha-methylstilbene

[0092] cis- and trans-4,4′-diphenylstilbene, diphenylethylene,dinaphthylethylene, 4,4′-vinylidenebis(N,N′-dimethylaniline),4,4′-vinylidenebis(amino-benzene), cis- and trans-stilbene,

[0093] trans-trans- and trans-cis- andcis-cis-1,4-diphenyl-1,3-butadiene

[0094] alpha,omega-tetraphenylpolyethyne

[0095] diphenylfulvene

[0096] triphenylethene

[0097] tetraphenylethene

[0098] 1-cyano-1-phenylethylene; 1-alkoxycarbonyl-1-phenylethylene; 1,1-dialkoxycarbonyl-2-ethylethylene;1,1-dialkoxycarbonyl-2-phenylethylene,1,1-dialkoxycarbonyl-2,2-dimethylethylene;1,1-dialkoxycarbonylmethylethylene; 9-methylenexanthene;9-methylenethioxanthene, 9-methylene-10-H-acridine or mixtures of two ormore thereof

[0099] are used as the compound of the formula (I) or (II).

[0100] According to the invention, the radical formation may be effectedby different methods. For example, thermal, photochemical,electrochemical or electron-transfer-induced production is just aspossible as the use of oxidizing or reducing agents for producingradicals.

[0101] In addition, the process described herein can be carried out inthe presence of at least one free radical initiator. Thermally,electrochemically or photochemically initiating monomers may also beused as initiators. In general, however, all azo and/or peroxo compoundsconventionally used in free radical chain polymerization and/orcompounds having homolytically cleavable C—C bonds may be used. Suitableinitiators are described, for example, on page 10, line 17 to page 11,line 15 of WO 98/01478, which is hereby fully incorporated in thecontext of the present application; in addition,3,4-dimethyl-3,4-diphenylhexane and 2,3-dimethyl-2,3-diphenylbutane maybe used. Preferably used initiators are those which are soluble in thereaction system used in each case, In the case of reaction in theaqueous phase, oxidizing free radical initiators, e.g. potassium, sodiumand ammonium peroxodisulfate, or a combination of a conventional, i.e.of a nonoxidizing, initiator with H₂O₂ are preferably used. Dicumylperoxide, dibenzoyl peroxide, dilauryl peroxide and AIBN may also beused.

[0102] In a preferred embodiment of the process a comparatively largeamount of free radical initiator is added, the amount of free radicalinitiator as a proportion of the reaction mixture preferably being from0.1 to 50, particularly preferably from 0.5 to 20, % by weight, based ineach case on the total amount of the monomer (a) and of the initiator.The molar ratio of initiator to compound (I) is preferably from 3:1 to1:3, particularly preferably from 2:1 to 1:2. in particular from 1.5:1to 1:1.5.

[0103] If the described reaction according to stage (i) is carried outin the aqueous phase, the term aqueous phase is understood in thecontext of the present text as meaning a phase which contains from 10 to100% by weight of water. If the amount of water in the aqueous phase isless than 10%, it is preferable in the context of the present inventionif the aqueous phase contains a mixture of water and one or morewater-miscible solvents, such as THF, methanol, ethanol, propanol,butanol, acetone, methyl ethyl ketone or the like. However, it is alsopossible to carry out the reaction according to stage (i) in thepresence of a mixture of water and a water-immiscible solvent, such asan aromatic solvent, for example toluene.

[0104] In a further embodiment, the above reaction according to stage(i) is carried out in the presence of at least one base. The lowmolecular weight bases used may be in principle all low molecular weightbases, NaOH, KOH, ammonia, diethanolamine, triethanolamine, mono-, di-or triethylamine, dimethylethanolamine or a mixture of two or morethereof being preferred and ammonia and di- and triethanolamine beingparticularly preferred.

[0105] However, it is also possible to carry out the reaction accordingto stage (i) in an organic solvent or in the absence of a solvent, forexample in the melt. When the term reaction in an organic solvent or inthe absence of a solvent is used in the context of the presentinvention, it is understood as meaning a reaction which takes place inthe presence of less than 10, preferably less than 5 or less than 1, %by weight of water. In a further embodiment of the present invention, atleast one block copolymer in whose preparation stage (i) was carried outin an organic solvent or in the absence of a solvent is used in thenovel binder composition, the water content of the reaction mixturebeing less than 0.5, for example less than 0.3 or less than 0.1, % byweight. In a further embodiment of the present invention, the reactionof stage (i) is carried out in the absence of water, i.e. with a watercontent of less than 0.001% by weight. Such water contents can beachieved, for example, by using commercially available solvents, asusually used as organic solvents in free radical polymerizations.

[0106] In the context of the present invention, suitable solvents are inprinciple all polar and nonpolar organic solvents in which thecorresponding polymers and preferably also the polymers formed aresoluble, if necessary at elevated temperature. Suitable solvents are,for example, C₃- to C₁₀-alkanes, cyclohexane, decalin, acetone, methylethyl ketone, diisobutyl ketone, tetrahydrofuran, dioxane, benzene,toluene, glycols such as ethylene glycol and triethylene glycol, glycolethers in which some or all of the terminal groups are blocked, such asethylene glycol monomethyl ether, ethyl acetate, methanol or ethanol orthe higher homologs of the alkanols of up to 18 carbon atoms (ifnecessary as cosolvent) or mixtures of two or more thereof.

[0107] The reaction according to stage (i) is generally carried out atabove room temperature and below the decomposition temperature of themonomers, preferably a temperature range from 50 to 200° C., furtherpreferably from 70 to 150° C., in particular from 80 to 120° C., beingchosen.

[0108] The reaction according to stage (i) is generally carried out atpressures from 1 to 300, for example from about 1.5 to 100 or from about2 to about 20, bar.

[0109] Although there are no restrictions at all regarding the molecularweight distribution, a reaction product which has a molecular weightdistribution M_(w)/M_(n), measured by gel permeation chromatographyusing polystyrene as standard, of ≦4, preferably ≦3, further preferably≦2, in particular ≦1.5 and in specific cases also ≦1.3 can be obtainedin the reaction according to (i). The molecular weight of the reactionproduct (A) can be controlled within wide limits by the choice of theratio of monomers (a) to compounds (I) to free radical initiator. Inparticular, the content of compound (I) determines the molecular weightand does so in such a way that the larger the amount of compound (I) thelower the molecular weight obtained.

[0110] The reaction according to stage (i) can also be carried out inthe presence of a surfactant.

[0111] The reaction product obtained in the reaction according to (i)can be further processed directly or can be used as a macroinitiator forthe further reaction according to stage (ii), as defined further belowherein. It is also possible to isolate the reaction product according tostage (i) as a solid and then to react it further or to use it.

[0112] At least one freely selectable monomer (b) capable of freeradical homopolymerization or copolymerization can be subjected to thereaction according to stage (ii), suitable monomers (b) being themonomers mentioned above in conjunction with the explanation of themonomers (a).

[0113] Monomer (b) may be identical to or different from the monomer (a)used in stage (i). It is of course also possible to use mixtures of twoor more monomers as monomer (a) or monomer (b). The choice of themonomer (b) is made in principle according to the desired structure ofthe polymer prepared in stage (ii) and hence depending on the desireduse of this polymer.

[0114] Specific examples are the following monomers (b) preferably to beused:

[0115] Styrene and derivatives, e.g. styrenesulfonic acid, methacrylicacid and acrylic acid, and the esters of these acids with methanol,ethanol, propanol (all isomers), butanol (all isomers), hexane (allisomers), vinyl acetate, hydroxyethyl acrylate, hydroxyethylmethacrylate, N-vinyl compounds, e.g. N-vinylpyrrolidone, and dienes,such as butadiene, isopiene, myrcene and pentadiene.

[0116] Accordingly, the present invention also relates to a process forthe preparation of a polymer (B), which comprises:

[0117] (ii) Reaction of the reaction product (A) obtained in stage (i),under free radical conditions, in the presence of at least one monomer(b) capable of free radical homopolymerization or copolymerization.

[0118] The reaction according to stage (ii) is carried out in principleunder the conventional conditions for a free radical polymerization orunder the conditions prevailing in stage (i) it being possible forsuitable solvents to be present.

[0119] In a further embodiment of the present invention, stage (ii) canbe carried out in the presence of compounds of the formula I or II,which are added after the end of stage (i).

[0120] In the process described herein, stages (i) and (ii) can becarried out separately from one another both in terms of space and interms of time, in which case, of course, stage (i) is carried out first,followed by stage (ii). In addition, however, stages (i) and (ii) canalso be carried out in succession in one reactor, i.e. first thecompound of the formula (I) is reacted completely or partially with atleast one monomer (a), depending on the desired use or the desiredproperties, and then at least one monomer (b) is added and is subjectedto free radical polymerization, or a monomer mixture comprising at leastone monomer (a) and at least one monomer (b) is used from the outset andis reacted with the compound (I). It is assumed that first the compound(I) reacts with the at least one monomer (a) and then the reactionproduct (A) formed therefrom also reacts with the monomer (b) above aspecific molecular weight. In this context, it should be noted inparticular that the novel (co)polymerization can be continued after anyinterruption without further addition of initiator, by heating to atemperature at which the macroinitiator formed according to reactionproduct (A) decomposes again.

[0121] The resulting polymer (reaction product (A)) can be isolated orcan be reheated in situ to initiate the (further) polymerization.Further monomer (b) can be identical to or different from monomer (a).It is also possible to use monomer mixtures from the outset. Stage (ii)can be repeated as often as desired, if necessary after isolation of therespective products in the individual stages.

[0122] Depending on the reaction procedure, it is possible according tothe invention to prepare polymers functionalized at the terminal groups,segmented polymers, block, multiblock or gradient (co)polymers, star(co)polymers, graft copolymers and branched and hyperbranched(co)polymers.

[0123] As is evident from the above, the present invention also relatesto the use of the polymer (B), which can be prepared by the processdefined above, for numerous applications. The reaction is preferablycarried out in such a way that a polymer (B) which has a block structureis obtained. Using an easily obtainable compound (I), it is possible ina simple manner to provide block copolymers which have, for example, ahydrophilic block, e.g. a (meth)acrylic acid or a C₁₋₄-alkyl(meth)acrylate block, and a fisher, preferably hydrophobic polymerblock, e.g. a block based on vinylaromatic monomers, such as styrene orsubstituted styrenes, acrylonitrile, dienes and nonaromatic vinylcompounds, such as vinyl acetate, and higher (>C₄) alkyl(meth)acrylates.

[0124] Polymers of the following structure are preferably used:

[0125] Poly((meth)acrylicacid-stat-(meth)acrylate-b-(styrene-stat-(meth)acrylate)), where theterm (meth)acrylate denotes alkyl esters of methacrylic acid or acrylicacid.

[0126] Specific examples are the following block copolymers:

[0127] Poly(acrylic acid-b-styrene), poly(methylmethacrylate-b-styrene), poly(styrene-b-vinyl acetate), poly(methacrylicacid-b-hydroxyethyl acrylate), poly(methylmethacrylate-b-N-vinylpyrrolidone), poly(methylmethacrylate-b-N-vinylformamide), poly(methylmethacrylate-b-hydroxyethyl acrylate), poly(methylmethacrylate-b-(styrene-stat-acrylonitrile)), poly(n-butylacrylate-b-styrene-b-n-butyl acrylate), poly(methylmethacrylate-b-styrene-b-methyl methacrylate-b-styrene), poly(n-butylacrylate-b-styrene-b-n-butyl acrylate-b-styrene), poly((meth)acrylicacid-stat-(meth)acrylate-b-(styrene-stat-(meth)acrylate)).

[0128] Specific examples are the following block copolymers:

[0129] Poly(styrene-b-acrylic acid), poly(styrene-b-methyl acrylate),poly(styrene-b-ethyl acrylate), poly(styrene-b-methacrylic acid),poly(styrene-b-methyl methacrylate), poly(styrene-b-ethyl methacrylate),poly(hydroxyethyl acrylate-b-methacrylic acid),poly(N-vinylpyrrolidone-b-methyl acrylate),poly(N-vinylpyrrolidone-b-ethyl acrylate),poly(N-vinylpyrrolidone-b-methyl methacrylate),poly(N-vinylpyrrolidone-b-ethyl methacrylate),poly(N-vinylpyrrolidone-b-styrene), poly(N-vinylpyrrolidone-b-vinylacetate), poly(N-vinylpyrrolidone-b-(α-methylstyrene),poly(N-vinylformamide-b-methyl methacrylate),poly(N-vinylformamide-b-ethyl methacrylate),poly(N-vinylformamide-b-vinyl acetate), poly(N-vinylformamide-b-methylacrylate) or poly(N-vinylformamide-b-ethyl acrylate).

[0130] The following can also be prepared according to the presentinvention:

[0131] Poly(methyl methacrylate-b-(styrene-stat-acrylonitrile),poly(n-butyl acrylate-b-styrene-b-n-butyl acrylate),poly(styrene-b-n-butyl acrylate-b-styrene), poly(styrene-b-n-butylacrylate-b-styrene-b-n-butyl acrylate), poly(methylmethacrylate-b-styrene-b-methyl methacrylate-b-styrene), poly(n-butylacrylate-b-styrene-b-n-butyl acrylate-b-styrene),poly(styrene-b-polybutadiene), poly(styrene-b-styrene-stat-butadiene),poly(styrene-stat-acrylonitrile-b-butadiene),poly-(styrene-stat-acrylonitrile-b-styrene-stat-butadiene),poly(styrene-stat-acrylonitrile-b-styrene-stat-acrylonitrile-stat-butadiene),poly(styrene-b-vinylpyrrolidone),poly(styrene-stat-acrylonitrile-vinylpyrrolidone), poly(n-butylacrylate-b-styrene), poly(n-butyl acrylate-styrene-acrylonitrile) andtheir ABA/ABC three-block polymers or higher block polymers and thelike.

[0132] As stated at the outset, the present invention relates to the useof the reaction products (A) and/or (B) described above for improving orproviding specific properties within application products. The reactionproducts (A) and/or polymers (B) described herein (often referred tobelow as components) can be used individually or as a mixture of two ormore thereof. Furthermore, it is possible to use the components as suchor in the form of solutions, suspensions, dispersions, emulsions, solidsor engineering material, and to do so as a function of the respectivemethod of use. The novel uses are described individually in detailbelow, reference being made where possible to publications in which theuse described herein has been described in principle with the use ofother polymers or reaction products.

[0133] Use as Component of Coating Materials, in Particular in Finishesand Surface Coatings

[0134] The reaction products (A) described herein and the polymer (B) ora mixture of two or more thereof can be used in the context of thepresent invention as a component of coating materials, in a formsuitable for this purpose, in particular as polymer dispersions.

[0135] In addition to said components (A) or (B), such coating materialscontain additives (C) suitable for their field of use, such as polymers,in particular crosslinking agents, crosslinking catalysts, initiators,in particular pigments, dyes, fillers, reinforcing fillers, rheologyassistants, wetting agents and dispersants, antifoams, adhesionpromoters, additives for improving substrate wetting, additives forimproving surface smoothness, dulling agents, leveling agents,film-forming assistants, drying agents, antiskinning agents, lightstabilizers, corrosion inhibitors, biocides, flameproofing agents,polymerization inhibitors, in particular photoinhibitors, orplasticizers, as are customary and known, for example, in the plasticsor leather sector. The choice of the additive depends on the desiredproperty profile of the coating material and its intended use.

[0136] These coating materials can be applied by the known methods ofapplication of liquid phases, such as dipping, spraying, knife coating,brushing, roller coating or pouring in the form of a liquid curtain.Examples of suitable substrates are films, sheets, fibers, metal sheets,woven fabrics or shaped articles, in particular automotive bodyworkcomponents, of metal, glass, wood, paper, plastics, leather, mineralsubstrates or composite materials thereof. During application, thesesubstrates may be stationary or moving, as, for example, in the coilcoating method.

[0137] Furthermore, such coating materials may be used in powder form,in particular in powder coating.

[0138] In particular, the coating materials may be components ofmultilayer coat structures, as encountered, for example, in automotiveOEM finishing, automotive refinishing, plastics coating, industrialcoating, container coating or the coil coating method or in furniturecoating.

[0139] Use as a Component in Toners

[0140] Toner compositions can be prepared by various known methods, forexample by mixing together and heating resin particles which contain thecomponents (A) or (B) described herein, for example correspondingstyrene/butadiene copolymers, with pigments, such as magnetite, carbonblack or mixtures thereof, and colored pigments, such as cyan, magenta,yellow, green, brown or red pigments or mixtures thereof, and preferablyfrom 0.5 to 5% by weight of an additive for increasing the charge in anextrusion apparatus for toners, for example ZSK 53 from Werner &Pfleiderer, and subsequently removing the resulting toner compositionfrom the apparatus. After cooling, the toner composition is milled in asuitable micronizing apparatus in order to obtain toner particles whichhave a mean diameter of less than about 25 μm, preferably from 6 to 12μm, these diameters being determined using a Coulter counter. This isfollowed by classification of the particles, toner particles having adiameter of less than 4 μm being removed.

[0141] Details regarding such toner compositions are disclosed, forexample, in U.S. Pat. No. 5,322,912, in particular in columns 11 to 15thereof, the content of which regarding the components of a tonercomposition are hereby fully incorporated in the context of the presentapplication.

[0142] Use as Component in Cosmetics

[0143] Reaction products (A) or polymers (B) having film-formingproperties are used in cosmetics as film formers for cosmetic,dermatological, hygiene and/or pharmaceutical formulations and areparticularly suitable as additives for hair and skin cosmetics.

[0144] In the cosmetic and dermatological formulations for the skin, thenovel reaction products (A) or polymers (B) are particularly effective.The reaction products (A) or polymers (B) can, inter alia, help to keepthe skin moist and to condition it and improve the feel of the skin.

[0145] The reaction products (A) or polymers (B) are preferably used forsetting and shaping the hair and improving its structure. They increasethe combability and improve the feel of the hair. These hair treatmentagents generally contain a solution of the film former in an alcohol ora mixture of alcohol and water.

[0146] One requirement of hair treatment agents is that they impart,inter alia, gloss, flexibility and a naturally pleasant feel to thehair.

[0147] In addition to the novel reaction products (A) or (B) andsuitable solvents, the cosmetic, dermatological, hygiene and/orpharmaceutical formulations can also contain conventional additives,such as emulsifiers, preservatives, perfume oils, cosmetic activeingredients, such as phytantriol, vitamins and provitamins, for examplevitamin A, E and C, retinol, bisabolol, panthenol, natural and syntheticlight stabilizers, natural substances, propellants, solubilizers,repellents, bleaches, coloring compositions, toning compositions,tanning compositions (for example dihydroxyacetone), micropigments, suchas titanium oxide or zinc oxide, reflectors, proteins, for examplewheat, almond or pea proteins, ceramide, ph-α-hydroxy acids, fruitacids, collagen, protein hydrolysis products, stabilizers, pHregulators, colors, salts, thickeners, gel formers, consistencyregulators, silicones, humectants, natural oil replenishers and furtherconventional additives.

[0148] Preferably, the novel reaction products (A) or polymers (B) areused as or in coating material(s) for keratin-containing andkeratin-analogous surfaces, such as hair, skin and nails.

[0149] In the formulation of hair setting compositions, it should beborne in mind that a reduction of the alcohol and propellant content isrequired owing to the environmental provisions for controlling theemission of volatile organic compounds (VOC) into the atmosphere.

[0150] Particularly suitable reaction products (A) or polymers (B) arethose which are water-soluble or whose water dispersibility is so highthat they are soluble in a 20:80 (V%/V%) water/ethanol solvent mixturein an amount of more than 0.1, preferably more than 0.2, g/l.

[0151] For example, the novel reaction products (A) or polymers (B) areused in cosmetic compositions for cleansing the skin. Such cosmeticcleansing compositions are selected from bar soaps, such as toiletsoaps, curd soaps, transparent soaps, luxury soaps, deodorant soaps,cream soaps, baby soaps, skin protection soaps, abrasive soaps andsyndets, liquid soaps, such as pasty soaps, soft soaps and wash pastes,and liquid washing, shower and bath preparations, such as wash lotions,shower compositions and gels, foam baths, oil baths and scrubpreparations and shaving foams, lotions and creams.

[0152] They are particularly suitable for hair cosmetics, preferably informulations such as hair repair treatments, hair lotions, hair rinses,hair emulsions, split end fluids, neutralizing compositions forpermanent waves, hot-oil treatment preparations, conditioners, settinglotions, shampoos, hair dyes or hair sprays.

[0153] The skin care compositions are present in particular as W/O orO/W skin creams, day and night creams, eye creams, face creams,antiwrinkle creams, moisturizing creams, bleaching creams, vitamincreams, skin lotions, care lotions and moisturizing lotions.

[0154] Depending on the field of use, the cosmetic, hygiene,dermatological and/or pharmaceutical formulations can be applied asspray (pump spray or aerosol), foam, gel, gel spray, lotion or mousse.

[0155] They are furthermore suitable for skin cosmetic formulations,such as face lotions, face masks, deodorants and other cosmetic lotions,and for use in decorative cosmetics, for example as a masking pen,theater paint, in mascara and eye shadow, lipsticks, kajal sticks,eyeliners, rouges, powders and eyebrow pencils.

[0156] The novel reaction products (A) or polymers (B) can also be usedin nose strips for pore cleansing, in antiacne compositions, repellents,shaving composites, depilatories, feminine hygiene compositions and footcare compositions and in baby care.

[0157] Furthermore, the novel reaction products (A) or polymers (B) aresuitable as excipients in pharmacy, preferably as or in coatingcomposition(s) or binder(s) for solid dosage forms. They can also beused in creams and as tablet coating compositions and tablet binders.

[0158] The novel reaction products (A) or polymers (B) are contained inthe cosmetic, dermatological or hygiene formulations in an amount offrom about 0.001 to 20, preferably from 0.1 to 10, % by weight, based onthe total weight of the composition.

[0159] Examples of particularly suitable solvents are water and lowermonoalcohols or polyols of 1 to 6 carbon atoms and mixtures thereof,preferred monoalcohols or polyols are ethanol, isopropanol, propyleneglycol, glycerol and sorbitol.

[0160] Further additives which may be present are fatty substances, suchas mineral and synthetic oils, for example paraffins, silicone oils andaliphatic hydrocarbons of more than 8 carbon atoms, animal and vegetableoils, for example sunflower oil, coconut oil, avocado oil, olive oil,lanolin or waxes, fatty acids, fatty esters, for example triglyceridesof C₆- to C₃₀-fatty acids, wax esters, such as jojoba oil, fattyalcohols, vaseline and hydrogenated lanolin. Mixtures thereof can ofcourse also be used.

[0161] Conventional thickeners in such formulations are crosslinkedpolyacrylic acid and its derivatives, polysaccharides, such as xanthangum, agar agar, alginates or tyloses, cellulose derivatives, for examplecarboxymethylcellulose or hydroxycarboxymethylcellulose, fatty alcohols,monoglycerides and fatty acids, polyvinyl alcohol andpolyvinylpyrrolidone.

[0162] After the polymerization of the novel reaction products (A) orpolymers (B), other polymers can also be admixed if specific propertiesare to be established.

[0163] Examples of conventional polymers suitable for this purpose areanionic, cationic, amphoteric and neutral polymers.

[0164] Use as Resin Material

[0165] Regarding the use of components (A) and (B) described herein asresin material, reference is made to DE-A 196 36 058, which describes astyrene resin material. It is of course also possible to prepare otherresin materials, for example polymers based on acrylic acid/butadieneand acrylic acid/styrene or acrylic acid/styrene/acrylic acid orcopolymers of styrene and acrylonitrile in the same or an analogousmanner. Such resin materials are described below using a styrene resinmaterial as an example.

[0166] According to the invention, the (co)polymers can be mixed with atleast one ether monomer. For example, the polymers described in EP-B 0512 951, in particular on page 4, line 6 to page 5, line 33, aresuitable for this purpose.

[0167] If desired, the resin material may contain lubricants, antistaticagents, antioxidants, heat stabilizers, ultraviolet absorbers, pigments,dyes, nucleating agents, rubbers, fillers, dulling agents, brighteningcompositions, flameproofing agents, blowing agents, mold release agentsand the additives and plasticizers, such as mineral oil, which arementioned in WO 97/27233, page 5, line 1 to page 5, line 37 and in EP-B0 512 95 1, page 6, lines 6-21 and page 7, lines 23-41.

[0168] According to the invention, the polymers stated in the presentapplication are used for processing to give moldings, sheets, fibers andfoams. The rheological and thermal behavior is critical for theperformance characteristics and processing properties. To ensure as faras possible trouble-free processing, it is important to keep the meltviscosity low, so that the polymers mentioned here, which have a lowviscosity, are particularly suitable.

[0169] Before they are processed to give moldings, sheets, fibers andfoams, the polymers arc generally mixed with additives which are usefulfor modifying the basic properties (modifiers, plasticizers, fillers andreinforcing materials, flameproofing agents, antistatic agents, dyes,pigments, etc.) or for carrying out the processing in a trouble-freemanner (stabilizers, lubricants, mold release agents, etc.). The novelpolymers used can also be employed as a mixture with other polymers,such as polyethylene terephthalate (PET), polybutylene terephthalate(PBT), polycarbonate (PC), polyamide (PA 6), polyamide 66 (PA 66),polyamide 12 (PA 12), polyamide 4,6 (PA 4,6), copolyamides,polypropylene oxide (PPO), polyetherimides, polyetherketones,polyimides, acrylonitrile/butadiene/styrene (polymers) (ABS),acrylonitrile/styrene/acrylate (polymers) (ASA), poly(amidoimides),polybutadiene, poly(meth)acrylate, epoxy resins, polyethylene (PE),polypropylene (PP), EPDM (ethylenepropylenediene monomer rubber),copolymers of α-olefins, polyvinyl chloride (PVC), polymethylmethacrylate (PMMA), polystyrene (PS), styrene/acrylonitrile copolymers(SAN), polyvinyl alcohol, polyvinyl acetate, thermoplastic polyurethaneelastomers (TPU), polylactide, and polymers described in chapter 5 ofPolymer Handbook, 3rd ed., Brandrup, J. and Immergut, E H, published byJohn Wiley & Sons, 1989, New York, and their blends and copolymers andblock copolymers. Further suitable additives and polymers are known tothose skilled in the art.

[0170] a) Compounding

[0171] The additives and further polymers are generally introduced withthe polymer mentioned here by compounding prior to processing, and thestarting materials are converted into a form ready for processing.Suitable compounding methods are mixing, if required subsequentroll-milling and kneading (plasticization) and, if required, subsequentgranulation.

[0172] b) Processing

[0173] The moldings, sheets, fibers and foams can be produced by variousmethods. In general, the polymers mentioned according to the presentapplication can be processed by means of any conventional method to givemoldings, sheets, fibers and foams. Suitable methods are describedbelow.

[0174] Processing Methods at Atmospheric Pressure

[0175] Processing methods at atmospheric pressure which are suitable,for example, for processing low-viscosity melts are casting, for examplemonomer casting and film casting, dipping, for example paste dipping,brushing and expansion.

[0176] Processing Under Pressure

[0177] In processing under pressure, a melt is first produced by theaction of heat and is then molded and is set by cooling. Suitableprocessing methods under pressure are pressing as well as rolling andcalendering, multistage roll mills with additional apparatuses beingrequired for shaping (melt rolling method, calendering), extrusion, bymeans of which, for example, continuous semifinished products, such aspipes, tubes, profiles, sheets, films, wire sheets, monofils, etc. and,after the extrusion process, hollow articles can be produced, and blowmolding methods for the production of closed hollow articles (e.g.toys), or hollow articles open at one end (e.g. bottles, containers)from tubular parisons, for example the abovementioned extrusion blowmolding method and injection blow molding method. A further importantprocessing method under pressure is injection molding, which permits theproduction of a multiplicity of complicated shapes.

[0178] The processing is preferably carried out by extrusion, blowmolding and injection molding, particularly preferably by injectionmolding.

[0179] In the processing of polymers by extrusion or blow molding, it isadvantageous if the polymers used have a low shear viscosity in themelt, i.e. the shear viscosity of the polymers during the melting in theextruder at high temperatures is low. In comparison, the shear viscosityat lower temperatures, when the molding material leaves the extruder,should be of the conventional order of magnitude.

[0180] During the processing of the polymers mentioned in the presentapplication by injection molding, it is advantageous that the polymershave a low viscosity in the melt.

[0181] c) Forming

[0182] The processing can, if required, be followed by a forming method.The non-cutting forming of semifinished products by the application ofexternal forces and heat serves for increasing the strength or forchanging the shape. Suitable forming methods are, for example,orientation (stretching) and heat setting, e.g., deep drawing, by meansof which semifinished products can be converted into sheets and tiles.The forming is preferably carried out by deep drawing.

[0183] Use as Retention Aid for Papermaking

[0184] The components (A) and (B) described herein can also be used asretention aids in the production of all paper grades and cardboards. Inthis context, reference is made to DE 197 19 059 and the paper gradesand cardboards described therein.

[0185] These components are preferably suitable for use in theproduction of paper from sulfite or sulfate pulp in the bleached orunbleached state, it being possible for this fiber material to containup to 100% by weight of groundwood and/or waste paper and therefore tohave a high proportion of mineral fillers, pigments and fibrous crill.

[0186] The components (A) and (B) are added to the paper stockdispersion in an amount of from 0.1 to 10, preferably from 0.5 to 5,particularly preferably from 1.0 to 3, % by weight, based on the drysolids content, upstream of the head box of the paper machine. Theaddition is made to the dispersion which may contain or to which hasbeen added, as fillers, calcium carbonate, kaolin, aluminum silicate andhydrated aluminum oxides, satin white, talc, gypsum, barite, calciumsilicate and lithopone, kieselguhr and synthetic, organic fillers fromthe recycled material.

[0187] The components (A) and (B) are advantageously added to the stockdispersion in the headbox, upstream of the vertical screen and upstreamor downstream of the stock pump, prior to sheet formation.

[0188] By using the components (A) and (B), excellent retention of thefillers is achieved and surprisingly impairment of the strength valuesis avoided in spite of the increase in the filler and hence in the ashcontent of the paper. This is particularly true for the use of stockdispersions which contain waste paper or mechanical pulps, such asgroundwood and thermomechanical pulp (TMP), or consist thereof

[0189] It was also found that, by using the components (A) and (B), theeffect of optical brighteners, which are added to improve the whitenessof the paper stock, is not adversely affected.

[0190] Use as Solubilizer in Pharmaceutical and Cosmetic Formulations

[0191] The components (A) and (B) described herein can also be used assolubilizers in pharmaceutical and cosmetic formulations.

[0192] Pharmaceutical and cosmetic formulations can be obtained byprocessing the components (A) and/or (B) with pharmaceutical or cosmeticactive ingredients by conventional methods and with the use of knownactive ingredients.

[0193] The pharmaceutical or cosmetic active ingredients used aresubstances which are is sparingly soluble in water and have a watersolubility of 10 g/l or less. The active ingredients may be from anyarea of indications. Examples here are benzodiazepines, antihypertensivedrugs, vitamins, cytostatic drugs, anaesthetics, neuroleptic drugs,antidepressants, antibiotics, antimycotic drugs, fungicides,chemotherapeutic drugs, urological drugs, platelet aggregationinhibitors, sulfonamides, spasmolytic drugs, hormones, immunoglobulins,sera, thyroid therapeutics, psychotropic drugs, antiparkinson drugs andother antihyperkinetic drugs, ophthalmic drugs, neuropathicpreparations, calcium metabolism regulators, muscle relaxants,narcotics, lipid depressants, hepathotherapeutic drugs, coronary drugs,cardiac drugs, immunotherapeutic drugs, regulatory peptides and theirinhibitors, hypnotics, sedatives, gynecological drugs, gout remedies,fibrinolytic drugs, enzyme preparations and transport proteins, enzymeinhibitors, emetics, drugs for stimulating blood flow, diuretics,diagnostic agents, corticoids, cholinergics, drugs for treatment of thebiliary ducts, antihistamines, broncholytics, beta receptor blockers,calcium antagonists, ACE inhibitors, arteriosclerotic drugs,antiphlogistic drugs, anticoagulants, antihypotensive drugs,antihypoglycemic drugs, antihypertensive drugs, antifibrinolytic drugs,antiepileptic drugs, antiemetics, antidotes, antidiabetic drugs,antiarrhythmic drugs, antianemic drugs, antiallergic drugs,anthelmintics, analgesics, analeptic drugs, aldosterone antagonists andslimming preparations.

[0194] The novel compounds are used as solubilizers in a known mannerFor example, the active ingredient is mixed with them and water isadded, if required with gentle heating, or the novel compounds aredissolved in water, if required with gentle heating, with simultaneousor subsequent addition of active ingredient.

[0195] Use as Incrustation Inhibitor and/or Soil Release Polymers inDetergents

[0196] The components (A) and/or (B) described herein, preferablycopolymers of the type described above which have been renderedhydrophobic, can also be used as incrustation inhibitors and/or soilrelease polymers in detergents. Regarding the general formulation ofsuch detergents and the function as incrustation inhibitor and/or soilrelease polymer, reference may be made to DE-A 196 08 044.

[0197] The components (A) and/or (B), preferably in a form renderedhydrophobic, are used as incrustation-inhibiting additives in amountsfrom 0.01 to 20% by weight in detergent powders. Their proportion of thetextile detergent powders is generally from 0.05 to 15% by weight.

[0198] Cleaning agents are to be understood as meaning, for example,cleaners for hard surfaces, for example for metal, plastics, glass andceramic cleaning, floor cleaners, sanitary cleaners, general-purposecleaners in the household and in commercial applications, industrialcleaners (for use in car washes or high-pressure cleaners), coldcleaners, dishwashing agents, rinse aids, disinfectant cleaners,cleaners for the food and beverage industry, in particular as bottlecleaners, as CIP cleaners (cleaning-in-place) in dairies, breweries andother facilities of food manufacturers. Cleaners which contain thepolymerization mixtures to be used according to the invention areparticularly suitable for cleaning hard surfaces, such as glass,plastics and metal. The cleaners may be alkaline, acidic or neutral.They usually contain surfactants in amounts from about 0,2 to 50% byweight. These may be anionic, nonionic or cationic surfactants ormixtures of surfactants which are compatible with one another, forexample mixtures of anionic and nonionic or of cationic and nonionicsurfactants. Alkaline cleaners may contain sodium carbonate, potassiumcarbonate, sodium bicarbonate, potassium bicarbonate, sodiumsesquicarbonate, potassium sesquicarbonate, sodium hydroxide, potassiumhydroxide, amine bases, such as monoethanolamine, diethanolamine,triethanolamine or ammonia, or silicate in amounts of up to 60% byweight and in some cases even up to 80% by weight. The cleaners mayfurthermore contain citrates, gluconates or tartrates, in amounts of upto 80% by weight. They may be present in solid or liquid form.

[0199] The components (A) and/or (B) to be used according to theinvention may be considered as cobuilders. Since they significantlyreduce the incrustation during the washing of textiles, they may also bereferred to as incrustation inhibitors. The detergents may be present inpowder form or as a liquid formulation. The composition of thedetergents and cleaning agents may be very different. Washing andcleaning formulations usually contain from 2 to 50% by weight ofsurfactant and, if required, builders. These data apply both to liquiddetergents and to detergent powders. Detergent and cleaning agentformulations which are commonly used in Europe, the USA and in Japan arelisted, for example, in a table in Chemical and Engn. News, 67 (1989),35. Further data on the composition of detergents and cleaning agentscan be obtained from Ullmanns Enzyklopädie der technischen Chemie,Verlag Chemie, Weinheim 1983, 4th edition, pages 63 to 160.

[0200] Reduced-phosphate detergents are to be understood as meaningthose formulations which contain not more than 25% by weight ofphosphate, calculated as pentasodium triphosphate. The detergents may beheavy-duty detergents or special detergents. Suitable surfactants areboth anionic and nonionic surfactants and mixtures of anionic andnonionic surfactants. The surfactant content of the detergents ispreferably from 8 to 30% by weight.

[0201] The surfactants present may be both anionic and nonionicsurfactants, reference being made to the abovementioned DE-A 196 08 044with regard to individual anionic and/or nonionic surfactants which maybe used.

[0202] In addition, the detergents in powder or granular form andpossibly also structured liquid detergents contain further componentscustomary in detergents, for example one or more inorganic builders,bleaches, enzyme systems, soil release polymers and/or antiredepositioninhibitors, reference likewise being made to DE-A 10 196 08 044 in thiscontext for further details on these components.

[0203] In connection with soil release polymers, it should be mentionedhere that the polymers (B) described herein are also particularlysuitable owing to the possibilities of modifying them in a virtuallyfreely selectable manner with regard to their properties in thepreparation process described here. For example, it is preferable to usein particular amphiphilic graft polymers or copolymers as describedherein, amphiphilic graft polymers or copolymers of vinyl esters and/oracrylates on polyalkylene oxides being mentioned in particular.

[0204] Use as Filtration Aid, for Clarifying Beverages

[0205] The components (A) and/or (B) described herein can also be usedas filtration aids and for clarifying beverages. In this context,reference may be made to EP-B 0 351 363, the content of which is herebyincorporated in full by reference in the context of the presentspecification. In this context, reference may be made in particular tothe section from column [lacuna], line 10 to column 6, line 29 of thispublication.

[0206] It is particularly advantageous to meter the filtration aid, i.e.the components (A) and (B) described herein, continuously into theunfiltered material. This can be realized in particular by metering inone operation or by metering in the crossflow circulation. It isadvantageous if the stabilizer is pumped with the circulation ofunfiltered material through the membrane filter of the crossflowfiltration unit. The circulation may be closed directly from the outletof the filtration unit via a pump back to the inlet thereof. However, itis also possible to close the circulation via the working tank, i.e. topump the unfiltered material continuously from the working tank throughthe membrane filter and to transport the retentate present at the outletof the filtration unit, together with the stabilizer contained therein,back into the working tank. Owing to the small pore size of suchcrossflow membrane filters (from 0.001 to 1 μm in the case ofultrafiltration or from about 0.1 to 1 μm in the case ofmicrofiltration), the entry of bound or precipitated tannins or proteinsinto the filtrate is reliably prevented. Instead, these are circulatedwith the retentate on the unfiltered material side of the membranefilter until the end of a filtration cycle.

[0207] The filtration aid may be metered in without recovery and removedfrom the filtration unit together with the sediments after the end of afiltration cycle. Polyvinylpolypyrrolidone (PVPP) and further blockcopolymers described herein and silica gel have proven particularlyuseful.

[0208] If the unfiltered material contains large amounts of suspendedmatter, the filtration performance of the membrane filters can beincreased if granular or fibrous filtration aids are fed to themembranes for protecting the membrane pores from blockage by sediments

[0209] Granular is understood as describing those filtration aids whichconsist of regularly or irregularly shaped particles which neitherdissolve in the unfiltered material nor agglomerate or are otherwisecompacted under the influence of the transmembrane pressure. Accordingto the invention, filtration aids consisting of such granular particlesare deposited in spite of the crossflow along the membrane surface andcan thus prevent the formation of continuous top layers of sediments.

[0210] The filtration aid can advantageously be applied as a top layerdirectly on the membrane surface. Consequently, the pores of themembrane surface are reliably protected from blockage by sediments. Thetop layer should have a layer thickness of 1 to 20 μm, preferably from 1to 8 μm; it therefore does not constitute a filter layer in theconventional sense but a protective layer for the actual membrane filterlayer.

[0211] The filtration aid can be applied to the membrane surface beforethe beginning of the filtration process. This produces a top layer whichconsists exclusively of the filtration aid and is free of contaminationby sediments. This can be achieved if first a medium which contains nosubstantial amounts of suspended matter is caused to flow across themembrane in order to start up a filtration cycle, if filtration aid isadded to the medium in order to form the top layer and if the unfilteredmaterial is then fed to the membrane. Such a top layer can be easilyproduced if the filtration cycle is started up with water to whichfiltration aid is added. As soon as the top layer has been produced, thewater can be forced out of the filter as a forward flow and unfilteredmaterial can be fed in.

[0212] In many applications, it may be advantageous if the filtrationaid is added to the unfiltered material. If, owing to the suspendedmatter present in the unfiltered material, there is no pronouncedtendency to rapid formation of top layers comprising sediment, thefiltration cycle can be started up in this way. A top layer of thefiltration aid then forms, in which certain amounts of sediment areincorporated. Alternatively, however, it is also possible, after theformation of a top layer comprising filtration aid, also to addfiltration aid continuously or batchwise to the unfiltered materialafter the startup with water or filtrate. The particles of thefiltration aid disturb any sediment layers so that they become morepermeable. Moreover, the granular filtration aid prevents the formationof compact layers, so that the crossflow can more readily dissolvesediment deposits.

[0213] The protection of the membrane pores from blockage is ensured ina particularly reliable manner if filtration aid having a particle sizewhich is greater than the pore size of the filter membrane is applied. Aparticle size of from 1 to 80 μm has proven particularly useful, and, byan appropriate choice of the particle size distribution, for examplefrom 60 to 80% of the particles in the range from 1 to 4 μm, it ispossible to optimize the filtration aid in this range with respect tothe medium to be filtered and the suspended matter contained therein,Particularly good permeability and a large filtration surface can beachieved if kieselguhr is used as filtration aid.

[0214] Regarding further details, reference may be made to EP-B 0 351363, as stated above.

[0215] Use as Components in Disinfectants

[0216] Regarding this use, reference may be made herein to EP-A 0 756820, which relates to the use of dextrins in disinfectants. However,these dextrins alone are not capable of forming sufficiently stableiodine complexes. Surprisingly, however, they can do so when mixed withthe reaction products (A) or the polymers (B) described herein, sincethese copolymers are likewise capable of taking up iodine, and are ableto do so with a bond force comparable to that of dextrin, for examplehomopolyvinylpyrrolidones and block copolymers of N-vinylpyrrolidone andstyrene, methyl methacrylate, methyl acrylate, hydroxymethyl acrylate orhydroxyethyl acrylate.

[0217] The disinfectants resulting therefrom have improved stability andconsequently also improved properties with respect to the disinfectantaction.

[0218] The formulations can be used in the form of ointments, solutions,shampoos, creams, soaps, gels or suppositories and in gelatin capsules,gargling solutions, sprays or sticks, such as lipsticks. Formulationshaving a pH of from 1 to 8, preferably from 2 to 7 and particularlypreferably from 3 to 6, are preferred.

[0219] According to the invention, it is also possible to preparetablets of a dextrin-containing iodophor. A particular advantage of thisis that, surprisingly, the iodophor, in contrast to known iodophors, isdirectly tabletable, i.e. can be compressed into tablets without furthertablet binders. In this way, binder-free iodophor tablets can beobtained in a simple and economical manner. If desired, small amounts ofadditives, such as lubricants, for example polyethylene glycols or fattyacid salts, such as magnesium stearate, can also be incorporated intothe tablets, as can disintegrants, for example crospovidone.

[0220] Effervescent tablets comprising dextrin-containing iodophor andalkali metal and/or alkaline earth metal bicarbonates or carbonates areparticularly advantageous. Because the tablet floats, the activesubstance can be more uniformly distributed in the water withoutstirring being necessary. This is particularly advantageous ifrelatively large amounts of water are to be treated, for example indrinking water treatment or in fish farming.

[0221] The dextrin-containing iodophors can also be processed to givepellets or granules without binders having to be added.

[0222] The tablets, pellets or granules can also be prepared assustained-release preparations having coats which dissolve slowly.

[0223] The formulations are suitable in particular for use in the coarsedisinfection of surfaces as well as fine disinfections. Thus, they canbe used in compositions for the antiseptic treatment of skin and mucousmembranes or for disinfecting hands for surgical and hygiene purposes.

[0224] The novel formulations are furthermore suitable for thepreparation of compositions for the treatment of skin disorders, such asdecubitus, varicose ulcers, dermatomycoses, pyodermia, acne andvaginitis, and for the treatment of burn wounds.

[0225] Furthermore, the novel formulations can be used in the area ofveterinary medicine, for example for disinfecting equipment, for udderdisinfection, in fish breeding, for example for disinfection of fisheggs, for disinfecting animal sheds, especially in chicken rearing, inparticular in egg laying. They are also suitable for the preparation ofdrugs for the treatment of diarrhea in animals.

[0226] Particularly when used in veterinary medicine or in animalbreeding, it is advantageous to use tablets, granules or pellets. Theseforms are more readily meterable than powders, avoid dust contaminationand can be administered directly or can be simply mixed with feed.

[0227] Use as Elastomeric Binders in Printing Plates

[0228] In this context, reference may be made to DE 2980246.8.

[0229] Examples of suitable elastomeric binders are elastomericpolymeric binders, for example polyalkadienes, vinylaromatic/alkadienecopolymers and block polymers, alkadiene/acrylonitrile copolymers,ethylene/propylene copolymers, ethylene/propylene/alkadiene copolymers,ethylene/acrylic acid copolymers, alkadiene/acrylic acid copolymers,alkadiene/acrylate/ acrylic acid copolymers and ethylene/(meth)acrylicacid/(meth)acrylate copolymers, in each case prepared as describedabove.

[0230] Elastomers which contain conjugated alkadienes, such as butadieneor isoprene, and styrene are very particularly suitable. The elastomericbinder is contained in the photopolymerizable cylinder layer in anamount of from 50 to 95, preferably from 50 to 90, % by weight based onthe total amount of the components contained in the cylinder layer.

[0231] Furthermore, the photopolymerizable relief-forming cylinder layerused according to the invention contains conventional and knowncopolymerizable ethylenically unsaturated organic compounds which arecompatible with the polymeric binder, in an amount from 1 to 60,advantageously from 2 to 50, in particular from 3 to 40, % by weight,based on the total amount of the cylinder layer. The term compatibleindicates that the relevant monomers are miscible with the elastomericbinder so readily that no haze or waviness is produced in the relevantphotopolymerizable relief-forming cylinder layer. Examples of suitablemonomers are the conventional and known acrylates and methacrylates ofmonohydric and polyhydric alcohols, acrylamides and methacrylamides,vinyl ethers and vinyl esters, allyl ethers and allyl esters anddiesters of fumaric acid or of maleic acid, in particular the esters ofacrylic and/or methacrylic acid with monohydric or preferably polyhydricalcohols, for example esters of acrylic or methacrylic acid withethanediol, propanediol, butanediol, hexanediol, oxaalkanediols, forexample diethylene glycol, or esters of acrylic or methacrylic acid withtrihydric or polyhydric alcohols, such as glycerol, trimethylolpropane,pentaerythritol or sorbitol, for example. Examples of particularlysuitable mono- and polyfunctional acrylates or methacrylates are butylacrylate, butyl methacrylate, 2-ethylhexyl acrylate, lauryl(meth)acrylate, hexanediol diacrylate, hexanediol dimethacrylate,ethylene glycol di(meth)acrylate, butanediol 1,4-di(meth)acrylate,neopentylglycol di(meth)acrylate, 3-methylpentanediol di(meth)acrylate,2-hydroxypropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate,1,1,1-trimethylolpropane tri(meth)acrylate, di-, tri- and tetraethyleneglycol di(meth)acrylate, tripropylene glycol di(meth)acrylate orpentaerythrityl tetra(meth)acrylate, and furthermore poly(ethyleneoxide) di(meth)acrylate, ω-methylpoly(ethyleneoxide)-α-yl-(meth)acrylate, N,N-diethylaminoethyl acrylate, a reactionproduct of 1 mol of glycerol, 1 mol of epichlorohydrin and 3 mol ofacrylic acid, and glycidyl methacrylate and bisphenol A diglycidyl etheracrylate.

[0232] Mixtures of photopolymerizable ethylenically unsaturated organiccompounds and, for example, mixtures of monofunctional (meth)acrylates,such as hydroxyethyl methacrylate, with polyfunctional (meth)acrylatesof the abovementioned type are also suitable.

[0233] In addition to the (meth)acrylates, derivatives of(meth)acrylamides, for example N-methylol(meth)acrylamidoethers ofpolyols (for example glycol), are also suitable.

[0234] In addition to the elastomeric binder and copolymerizableethylenically unsaturated monomeric compounds the cylinder layercrosslinkable by actinic radiation (=photosensitive recording layer)contains one or more photoinitiators, for example benzoin or benzoinderivatives, such as benzoin ethers of straight-chain or branchedmonoalcohols of 1 to 6 carbon atoms, for example benzoin methyl, ethyl,isopropyl, n-butyl or isobutyl ether, symmetrically or asymmetricallysubstituted benzil acetals, such as benzil dimethyl acetal, benzil1-methyl 1-ethyl acetal, diarylphosphine oxides, such as2,4,6-trimethylbenzoyldiphenylphosphine oxide or2,6-dimethoxybenzoyldiphenylphosphine oxide or acyldiarylphosphineoxides according to German Laid-Open Application DE-OS 2,909,992, orhydroxypropanones, such as 1-phenyl-2-methyl-2-hydroxy-1-propanone and1-hydroxycyclohexyl phenyl ketone. They may be used alone or as amixture with one another or in combination with coinitiators, forexample benzoin methyl ether with triphenylphosphine, diacylphosphineoxides with tertiary amines or acyldiarylphosphine oxides with benzildimethyl acetal.

[0235] In the mixtures they are used in an amount from 0.001 to 10,advantageously from 0.1 to 5, in particular from 0.3 to 2, % by weight,based on the total amount of the photosensitive cylinder layer, theamount being determined by, inter alia, the presence ofphotopolymerizable monomers.

[0236] Thermal polymerization inhibitors which have no significantself-absorption in the actinic range in which the photoinitiator absorbscan be added as further assistants which may be present, in general inan amount from 0.001 to 2% by weight, based on the total amount of thephotosensitive cylinder layer, for example 2,6-di-tert-butyl-p-cresol,hydroquinone, p-methoxyphenol, β-naphthol, phenothiazine, pyridine,nitrobenzene, m-dinitrobenzene or chloranil; thiazine dyes, such asthionine blue G (C.I. 52025), methylene blue B (C.I. 52015) or toluidineblue (C.I. 52040); or N-nitrosamines, such as N,N-nitrosodiphenylamine,or the salts, for example the potassium, calcium or aluminum salts, ofN-nitrosocyclohexylhydroxylamine.

[0237] Suitable dyes, pigments or photochromic additives may also beadded to the photosensitive mixture of the recording layer, in an amountfrom 0.0001 to 2% by weight, based on the mixture,

[0238] The preparation of the photopolymerizable relief-forming cylinderlayer used according to the invention from its components is carried outin general by mixing the components with the aid of known mixing methodsor by processing the mixture for the IR-sensitive layer with the aid ofknown techniques, such as casting from solution, calendering orextrusion, it also being possible for these measures to be combined withone another in a suitable manner.

[0239] The cylinder layer crosslinkable by actinic radiation generallyhas a thickness of from 200 to 8000 μm, in particular from 500 to 6000μm. A further thin layer which may have a thickness of from 1 to 5 μmand which detackifies the surface of the photosensitive cylinder layermay be applied thereon. Present on the latter or preferably directly onthe cylinder layer crosslinkable by actinic radiation is theIR-sensitive layer, which is a layer which is soluble or dispersible indevelopers and contains, in a film-forming binder having elastomericcharacter, at least one finely divided substance which has highabsorption in the wavelength range from 750 to 20,000 nm and an opticaldensity ≧2.5 in the actinic range. Developers may be water andwater/alcohol or organic solvent (mixtures). Suitable binders havingelastomeric character for the IR-sensitive layer are polymers, inparticular copolymers, which are either water-soluble or dispersible inwater or water/alcohol mixtures or those which are soluble ordispersible in organic solvents or solvent mixtures. Suitable alcoholsin the water/alcohol mixtures are methanol, ethanol, n-propanol andisopropanol.

[0240] Examples of binders which are soluble or dispersible in water orin water/alcohol mixtures and have elastomeric character are polyvinylalcohol/polyethylene glycol graft copolymers (for example Mowiol® 597from Hoechst Aktiengesellschaft, Germany), which are obtainable bygrafting vinyl acetate onto polyehtylene glycol having molecular weightsof from 1000 to 50,000 and then carrying out hydrolysis to a degree ofhydrolysis of from 90 to 100%.

[0241] Examples of binders which are soluble or dispersible in organicsolvents or solvent mixtures and have elastomeric character arethermoplastic polyamide resins which can be prepared, for example, byconventional polycondensation and are marketed, for example, under thename Macromelt® by Henkel KGaA, Germany. All of the abovementionedproducts are described in detail in the respective relevant companypublications.

[0242] The film-forming binders having elastomeric character and presentin the IR-sensitive layer contain finely divided substances which have ahigh absorption in the IR range. Examples of such substances are variousfinely divided carbon black grades, for example pigment black FW2000,special black 5, Printex® U from Degussa Aktiengesellschaft, Germany,having a mean primary particle size of from 13 to 30 nm. Advantageouslyused solutions are those which contain binders having elastomericcharacter and substances having high IR absorption, which solutions areeither applied uniformly and directly onto the cylinder layer and driedor cast to give a film, dried and laminated with the cylinder layer. Thefilm can, if required, be peeled off.

[0243] It is also possible to apply a peelable film transparent toactinic light, a cover sheet which has a thickness of from 5 to 300 μm,which consists, for example, of polyethylene or polyethyleneterephthalate, to the IR-sensitive layer.

[0244] Synthetic oligomers or resins, such as oligostyrene, oligomericstyrene/butadiene copolymers, oligomeric α-methylstyrene/p-methylstyrenecopolymers, liquid oligobutadienes, liquid oligoisoprenes or liquidoligomeric acrylonitrile/butadiene copolymers, each prepared asdescribed above, may also be used. Such oligomers are molecules having amolecular weight of from 500 to 5000 g/mol.

[0245] Use as Dispersants, Preferably as Dispersants in Inkjet PigmentFormulations

[0246] The components (A) and (B) described here are extremely usefulfor the preparation of aqueous dispersions and perform the function of adispersant. In this context, reference may be made to DE-A 100 05 648.

[0247] If components (A) and (B) are used as dispersants, then, forexample, aqueous dispersions which have excellent long-term stabilitycan be obtained therefrom. Depending on the intended use of thedispersions thus obtainable, the amount of these components in the totalaqueous dispersion can vary within wide ranges. If the components areused, for example, as dispersants for stabilizing a dispersion whichcontains a solid which is not self-dispersible, the amount of the novelcompounds used may be from about 0.01 to about 40, for example fromabout 0.1 to about 20 or from about 0.5 to about 10 or from about 1 toabout 5, % by weight. The amount of solids in such a dispersion can varyover a wide range. Depending on the intended use, it is thereforepossible to use the novel compounds to obtain dispersions which have asolids content of up to about 99% by weight. Particularly when suchdispersions are to be used for coating surfaces, they preferably have asolids content of from about 30 to about 95, for example from about 40to about 90 or from about 50 to about 80, % by weight.

[0248] The present invention therefore also relates to aqueousdispersions, at least containing one of the components (A) and (B).

[0249] In a further preferred embodiment, however, these components arealso suitable as the sole component of such a dispersion, in particularas the disperse phase of an aqueous dispersion. Such dispersions can beused, for example, as coating materials for the production of surfacecoatings. When used in this manner, it is advantageous if the componentused is a compound which, after removal of the continuous phase, gives asurface coating which corresponds to the user's requirements. When usedin this manner, it is therefore preferable, according to the invention,if the novel compound used is a compound having a molecular weight of atleast about 1000.

[0250] In addition to water and one of the components, or a mixture oftwo or more thereof, the novel aqueous dispersions may also contain oneor more further compounds.

[0251] If the novel aqueous dispersion is to be used as a surfacecoating material, the dispersion may contain, for example, at least onepolymer which is obtainable by polymerization of monomers havingethylenically unsaturated double bonds. Suitable monomers are, forexample, acrylic acid, methacrylic acid, acrylonitrile, acrylates ormethacrylates, as obtainable by esterifying acrylic acid or methacrylicacid with methanol, ethanol, n-butanol, isobutanol, or 2-ethylhexylalcohol, vinyl esters of carboxylic acids of 1 to 16 carbon atoms or1-alkenes, such as ethylene, propylene or butylene, or styrene. Suchpolymers may, for example, already be in dispersed or at leastpolymerized form when mixed with the novel dispersion. However, it isalso possible to prepare said polymers in the novel aqueous dispersion.Here, the respective compounds and reaction conditions can be chosen sothat, for example, at least a part of the polymers produced in thedispersion are added, by means of a grafting reaction, to the novelcompounds present in the dispersion. Corresponding polymers are preparedby methods known to those skilled in the art, as described, for example,in D. C. Blackley, Emulsion Polymerization—Theory and Practice, London,Applied Science Publishers, 1975, or in H. Warson, Application ofSynthetic Resin Emulsions, London, Benn Publishers, 1972, or in I.Piirma, Emulsion Polymerization, New York, Academic Press Inc., 1982.

[0252] The novel dispersions may furthermore contain additives, such asorganic solvents, pigments, dyes, emulsifiers, surfactants, thickeners,stabilizers, leveling agents, fillers, sedimentation inhibitors,flameproofing agents, UV stabilizers or antioxidants.

[0253] Suitable solvents are, for example, acetone, methyl ethyl ketone,tetrahydrofuran, dimethylformamide, dimethylacetamide, dioxane, ethylacetate and the like, or a mixture of two or more thereof. The noveldispersions may contain the organic solvents in an amount of up to about20, preferably up to about 10, % by weight.

[0254] Other suitable thickeners in addition to the novel components (A)and (B) themselves are polymers of hydrophilic monomers capable of freeradical polymerization, such as acrylic acid or methacrylic acid,polyvinylpyrrolidone or thickeners based on cellulose or starchderivatives, such as carboxymethylcellulose, carboxyethylcelluse,hydroxyethylcellulose, hydroxypropylcellulose, hydroxyethyl starch,hydroxypropyl starch and the like, Said thickeners may each be presentindividually or as a mixture of two or more thereof in the noveldispersions.

[0255] Suitable fillers or pigments are, for example, titanium dioxide,antimony oxide, zinc oxide, basic lead carbonate, basic lead sulfate,barium carbonate, porcelain powder, clay, aluminum silicate, silica,magnesium carbonate, magnesium silicate or calcium carbonate. Forexample, cadmium yellow, cadmium red, carbon black, phthalocyanine blue,chromium yellow, toluidyl red and hydrated iron oxide may be used ascolored pigments.

[0256] The novel dispersions are prepared by generally customary methodsknown to those skilled in the art. Suitable methods are described, forexample, in Kunststoffhandbuch, No. 7, Polyurethane, Carl Hanser Verlag,1993.

[0257] The novel aqueous dispersions can be used in particular assurface coating materials. In this respect, they may be combined with amultiplicity of substrates. Examples of suitable substrates are wood,metal, glass, textiles, leather, paper, plastics and the like. The novelaqueous dispersions can be applied by any desired, conventional methods,such as dipping, spraying, knife coating, brush application or the like.

[0258] The present invention furthermore relates to the use of at leastone of the components (A) and (B) as wetting agents, dispersants,surfactants, adhesion promoters, assistants in electroplating baths,acid catalysts in chemical syntheses or curing components in coatingmaterials.

[0259] The novel polymeric dispersants, as an individual substance or asa mixture, are particularly suitable for wetting, dispersing andstabilizing pigments in aqueous or solvent-containing suspensions. Ithas been found that the novel dispersants lead to good fixing of thepigments on, in particular, cellulosic fibers, which is confirmed byexcellent wet and dry abrasion resistances. The pigments can be selectedfrom among colored pigments or magnetic pigments.

[0260] Regarding this use, reference may be made to DE-A 19842952.5,which is hereby fully incorporated by reference in the context of thepresent application.

[0261] This publication also lists, for example, suitable pigments, suchas monoazo pigments, diazo pigments, vat dyes, inorganic pigments andmagnetic pigments.

[0262] Expediently, the pigments are first converted with the noveldispersant into a suitable form for use, a pigment formulation. Thepigment formulations can be used directly, for example as print paste orink, or can be used for the preparation of a form for use, for example awriting ink or inkjet ink. The pigment formulations can be incorporatedinto aqueous or organic systems simply and without undesirableflocculation. For the preparation of the pigment formulations, thepigments are mixed with the novel dispersants and, if desired, furtheradditives in the presence of a diluent, such as water. For liquidpreparation, in which the pigment is finely distributed in the presenceof relatively large amounts of diluent, in particular dissolvers forpredispersing and stirred ball mills are suitable, such as bead millsgenerally and those having small grinding beads (having, for example, adiameter of 0.3 mm), such as the double-cylinder bead mills (DCP-SuperFlow® from Draiswerken GmbH, Mannheim, or the centrifugal fluidized-bedmills (ZWM) from Netzsch Gerätebau GmbH, Selb. In this way, finelydivided and low-viscosity pigment formulations are obtained. Comparedwith conventional dispersants, the novel dispersant leads toadvantageously high flowabilities and stable storage behavior. Whenpigment formulations prepared using the novel dispersant were stored, nosettling of the pigment was observed over months.

[0263] Moreover, the novel dispersant can be used universally for amultiplicity of different pigments.

[0264] Alternatively, the pigment can be processed with the dispersant,with or without heating, to give a plastic material. Mixers andplasticating apparatuses, such as kneaders, extruders and/or roll mills,are particularly suitable for this purpose.

[0265] The pigment contained in the pigment formulation after dispersingshould be very finely divided. Preferably 95%, particularly preferably99%, of pigment particles have a particle size of <1 μm, preferably <5μm.

[0266] The novel pigment formulations contain, as a rule, from 0.1 to35, preferably from 0.1 to 20, particularly preferably from 0.2 to 10, %by weight of pigment.

[0267] Water is the main component of the novel pigment formulations.Its content is as a rule from 35 to 90, preferably from 45 to 80, % byweight.

[0268] The novel pigment formulations preferably also contain ahumectant, reference once again being made here to DE-A 19842952.5 withregard to examples of such humectants. Suitable humectants in additionto polyhydric alcohols, in particular of 3 to 8 carbon atoms, such asglycerol, erythritol or pentaerythritol, are pentitols, such asarabitol, adonitol and xylitol, and hexitols, such as sorbitol, mannitoland dulcitol, especially polyalkylene glycols and polyalkylene glycolmonoalkyl ethers, which are also to be understood as meaning the lower(di-, tri- and tetra-)alkylene glycols and alkylene glycol ethers. Thesecompounds preferably have average molecular weights of from 100 to 1500,polyethylene glycols and polyethylene glycol ethers having an averagemolecular weight of <800 being particularly preferred.

[0269] Of course, the novel pigment formulations may contain furtherassistants, as are customary in particular for (aqueous) inkjet inks andin the printing and coatings industry. Examples which may be mentionedare preservatives (such as 1,2-benzoisothiazolin-3-one and its alkalimetal salts, glutardialdehyde and/or tetramethylolethyleneurea),antioxidants, degassers/antifoams (such as acetylenediols andethoxylated acetylenediols, which usually contain from 20 to 40 mol ofethylene oxide per mole of acetylenediol and at the same time have adispersant effect, or phosphoric acid/alcohol mixtures), compositionsfor regulating the viscosity, leveling agents, wetting agents,antisettling agents, gloss improvers, lubricants, adhesion improvers,antiskinning compositions, dulling agents, emulsifiers, stabilizers,water repellents, light-stabilizing additives, handle improvers andantistatic agents. If these compositions are components of the novelpigment formulations, their total amount is as a rule ≦1% by weight,based on the weight of the formulation.

[0270] The novel pigment formulations usually have a dynamic viscosityof from 1 to 20, preferably from 1 to 5, mm²/sec.

[0271] The surface tension of the novel pigment formulations is as arule from 20 to 70, preferably from 35 to 60, mN/m.

[0272] The pH of the novel pigment formulations is in general from 5 to11, preferably from 7 to 9.

[0273] In the preparation of the novel pigment formulations, it isexpedient to proceed as follows:

[0274] The pigment, for example in the form of a water-containing presscake or in the form of a dry pigment powder, is mixed together with oneor more novel dispersant(s) in the presence of water and predispersed ina suitable apparatus. The mixture obtained is then milled in a mill inorder to establish the desired pigment particle size distribution, afterwhich further assistants are added. Finally, the final formulation isprepared by adding corresponding amounts of water and, if required, oneor more humectants and, if required, further assistants, mixing and thenfixing by means of a filtration apparatus with fines removal in therange from, as a rule, 10 to 1 μm and preferably then by means of afurther filtration apparatus with fines removal in the range from 1 to0.5 μm.

[0275] The novel pigment formulations can advantageously be used in thelikewise novel process for the printing of sheet-like orthree-dimensional substrates by the inkjet printing method, wherein thepigment formulations are printed onto the substrate and the printobtained is then fixed.

[0276] In the inkjet method, usually aqueous inks in small droplets aresprayed directly onto the substrate. A distinction is made between acontinuous method in which the ink is forced uniformly through a nozzleand is guided by an electric field, depending on the pattern to beprinted, onto the substrate, and an interrupted inkjet or drop-on-demandmethod in which the ink is ejected only where a colored dot is to bepositioned. In the last-mentioned method, pressure is exerted on the inksystem either by means of a piezoelectric crystal or by means of aheated cannula (bubblejet or thermojet method) and an ink droplet isthus forced out. Such procedures are described in Text. Chem. Color,Volume 19 (88), pages 23 to 29, 1987, and Volume 21 (6), pages 27 to 32,1989.

[0277] The novel pigment formulations are particularly suitable as inksfor the bubblejet method and for the method by means of a piezoelectriccrystal.

[0278] The novel pigment formulations can be printed on all types ofsubstrate materials. Examples of substrate materials which may bementioned are

[0279] cellulose-containing materials, such as paper, board, cardboard,wood and woodbase materials, which may also have been treated with afinish or otherwise coated,

[0280] metallic materials, such as foils, sheets or workpieces made ofaluminum, iron, copper, silver, gold, zinc or alloys of these metals,which may have been treated with a finish or otherwise coated,

[0281] silicate materials, such as glass, porcelain and ceramic, whichmay likewise have been coated,

[0282] polymeric materials of any type, such as polystyrene, polyamides,polyesters, polyethylene, polypropylene, melamine resins, polyacrylates,polyacrylonitrile, polyurethanes, polycarbonates, polyvinyl chloride,polyvinyl alcohols, polyvinyl acetates, polyvinylpyrrolidones andcorresponding copolymers and block copolymers, biodegradable polymersand natural polymers, such as gelatin,

[0283] textile materials, such as fibers, yarns, thread, knits, wovens,nonwovens and ready-made goods composed of polyester, modifiedpolyester, polyester blend fabrics, cellulose-containing materials, suchas cotton, cotton blend fabrics, jute, flax, hemp and ramie, viscose,wool, silk, polyamide, polyamide blend fabrics, polyacrylonitrile,triacetate, acetate, polycarbonate, polypropylene, polyvinyl chloride,polyester microfibers and glass fiber fabric,

[0284] leather, both natural and artificial, in the form of smoothleather, nappa leather or suede leather,

[0285] food and cosmetics.

[0286] The substrate material may be sheet-like or three-dimensional andmay be printed with the novel pigment formulations both uniformly andimagewise.

[0287] The novel pigment formulations are extremely useful for theproduction of writing inks and of toners, in particular of aqueous,liquid toners, and of toner powders.

[0288] The toners can be produced, for example, conventionally bymixing, kneading, milling and screening pigments with the polymericdispersants.

[0289] Use as Excipients in a Tablet Matrix

[0290] The components (A) and (B) described herein are also suitable forformulating active ingredients for drugs, crop protection agents, feedsand foods and also feed supplements and food supplements, fragrances andperfume oils, where the proportion by weight of said components in thefinal formulation may be from 1 to 99% by weight. It is of course alsopossible to use mixtures of different components or mixtures of thecomponents with farther polymers and/or different active ingredients.

[0291] Possible additional formulation excipients are

[0292] a) meltable sugar alcohols, sugars, fats and waxes (from 0 to99%),

[0293] b) polymers, such as polyvinylpyrrolidone, cellulose derivatives,polyvinylformamide (also partially or completely hydrolyzed),copolymers, polyethylene glycols, starch and starch derivatives,polyacrylates and polymethacrylates (Eudragit types), polyvinyl alcohol,partially hydrolyzed polyvinyl acetate and polyacrylamides (from 0 to99%),

[0294] c) if required, assistants such as surfactants, disintegrants,colorants, lubricants or plasticizers, dispersants, fillers or salts andantifoams (from 0 to 99%) or other mixtures.

[0295] Other pharmaceutical excipients are added bases or acids forcontrolling the solubility of an active ingredient.

[0296] There are no restrictions at all with regard to the activeingredients which can be formulated with the components described here.Examples which may be mentioned are benzodiazepines, antihypertensivedrugs, vitamins, cytostatic drugs, anesthetics, neuroleptics,antidepressants, antibiotics, antimycotic drugs, fungicides,chemotherapeutic drugs, urological drugs, platelet aggregationinhibitors, sulfonamides, spasmolytic drugs, hormones, immunoglobulins,sera, thyroid therapeutics, psychotropic drugs, antiparkinson drugs andother antihyperkinetic drugs, ophthalmic drugs, neuropathicpreparations, calcium metabolism regulators, muscle relaxants,narcotics, lipid depressants, hepatotherapeutic drugs, coronary drugs,cardiac drugs, immunotherapeutic drugs, regulator peptides and theirinhibitors, hypnotics, sedatives, gynecological drugs, antigout drugs,fibrinolytic drugs, enzyme preparations and transport proteins, enzymeinhibitors, emetics, compositions for promoting blood flow, diuretics,diagnostic drugs, corticoids, cholinergic drugs, drugs for the treatmentof biliary ducts, antihistamines, broncholytic drugs, beta receptorblockers, calcium antagonists, ACE inhibitors, arteriosclerotic drugs,antiphlogistic drugs, anticoagulants, antihypotensive drugs,antihypoglycemic drugs, antihypertensive drugs, antifibrinolytic drugs,antiepileptic drugs, antiemetics, antidotes, antidiabetic drugs,antiarrhythmic drugs, antianemic drugs, antiallergic drugs,anthelmintics, analgesics, analeptics, aldosterone antagonists andslimming preparations.

[0297] Pharmaceutical and other formulations can be obtained byprocessing the components (A) and/or (B) with pharmaceutical or otheractive ingredients by conventional methods and with the use of knownactive ingredients.

[0298] In the preparation of the formulations, it is of course alsopossible to add further excipients conventionally used in thepreparation of solid oral dosage forms. These may be substances fromamong fillers and binders (for example lactose, calcium phosphates,cellulose and its derivatives, starch, polyvinylpyrrolidone,polyvinylformamide (also partially or completely hydrolyzed), polyvinylalcohol, partially hydrolyzed polyvinyl acetate, polyacrylamides (from 0to 99%), sugar alcohols, sugars, fats or waxes (from 0 to 99%)),

[0299] disintegrants (for example Kollidon C L, according to the claimcarboxymethyl starch or carboxymethylcellulose),

[0300] lubricants (for example magnesium stearate, calcium behenate,stearic acid or PEG),

[0301] flow regulators (for example finely divided silica),

[0302] film formers (for example polyacrylates and polymethacrylates(Eudragit types),

[0303] copolymers based on acrylate derivatives,hydroxypropylmethylcellulose, hydroxypropylcellulose, cellulose acetate,cellulose acetate phthalate and other coating materials resistant togastric fluid),

[0304] humectants (for example glycerol, propylene glycol, sorbitol,mannitol or polyethylene glycols),

[0305] plasticizers, colorants, surfactants, salts and dispersants.

[0306] Use as Assistants for Plasticizing Concrete

[0307] Regarding this use, reference may be made to DE-A 196 53 524,whose content in this respect is hereby fully incorporated by referencein the context of the present application. Reference may be made inparticular to the section of this patent application beginning on page10, line 51 to page 11, line 37.

[0308] The novel components (A) or (B) are extremely useful as additivesfor cement mixes, such as concrete or mortar. Cement is to be understoodas meaning, for example, Portland cement, high-alumina cement or mixedcement, for example pozzolanic cement, slag cement or other types.Portland cement is preferred. The copolymers are used in an amount offrom 0.01 to 10, preferably from 0.05 to 3, % by weight based on theweight of the cement.

[0309] The components (A) and (B) can be added in solid form, which isobtainable by drying, for example spray-drying, of polymer solutions ordispersions as obtained in the polymerization, to the ready-to-usepreparation of the mineral building material. It is also conceivable toformulate the copolymers with the mineral binder and to prepare theready-to-use preparation of the mineral building materials therefrom.Preferably, the copolymer is used in liquid, i.e. dissolved, emulsifiedor suspensed, form, for example in the form of the polymerizationsolution, in the preparation of the mineral building material.

[0310] For use in concrete and mortar, it may be advantageous to employpolymers which are converted into a water-soluble and hence active formonly in the presence of the alkaline concrete or mortar, for examplepolymers containing carboxylic acid or carboxylic anhydride structures.The slow release of the active polymer results in a longer-lastingactivity.

[0311] The novel components (A) and (B) can also be used in combinationwith the known concrete plasticizers based on the sulfonate of anaphthalene/formaldehyde condensate, the sulfonate of amelamine/formaldehyde condensate, a phenolsulfonic acid/formaldehydecondensate and ligninsulfonates. They can also be used in combinationwith high molecular weight polyethylene oxides (molecular weight from100,000 to 8,000,000). Furthermore, they can be used together withcelluloses, for example alkyl- or hydroxyalkylcelluloses, starches orstarch derivatives. Additives such as air pore formers, expansioncompositions, water repellents, setting retardants, settingaccelerators, antifreezes, sealants, pigments, corrosion inhibitors,flowability additives, grouting aids, stabilizers and hollowmicrospheres may furthermore be admixed.

[0312] In principle, the novel components (A) and (B) can also be usedtogether with film-forming polymers. These are understood as meaningthose polymers whose glass transition temperature (DSC midpointtemperature, ASTM D 3481-82) is ≦65° C., preferably ≦50° C.,particularly preferably 25° C., very particularly preferably ≦0° C. Onthe basis of the relationship between the glass transition temperatureof homopolymers and the glass transition temperature of copolymers,postulated by Fox (T. G. Fox, Bull. Am. Phys. Soc. (Ser.II) 1 (1956),123), those skilled in the art are able to select suitable polymers(glass transition temperatures for homopolymers are to be found, forexample, in Ullmanns Encyclopedia of Industrial Chemistry, Vol. A21,VCH, Weinheim 1992, page 169, or in J. Brandrup, E. H. Immergul, PolymerHandbook, 3^(rd) Ed., J. Wiley, New York 1998).

[0313] Furthermore, it is often advantageous if the novel components (A)and (B) are used together with antifoams. This prevents too much airfrom being introduced into the concrete in the form of air pores duringthe preparation of the ready-to-use building materials, which air poreswould reduce the strength of the set mineral building material. Suitableantifoams comprise in particular polyalkylene oxide-based antifoams,such as polyethylene oxide, polypropylene oxide, dialkyl ethers, such asdiethylene glycol heptyl ether, polyethylene oxide oleyl ether,polypropylene oxide dibutyl ether, polyethylene oxide 2-ethylhexyl etheror polypropylene oxide 2-ethylhexyl ether. Also suitable are theethoxylation products and the propoxylation products of alcohols of 10to 20 carbon atoms, ethoxylated/propoxylated (alkyl)phenol, such aspropoxylated phenol (degree of propoxylation from 2 to 40) andethoxylated (alkyl)phenol (degree of ethoxylation from 2 to 50). Thediesters of alkylene glycols or polyalkylene glycols, such as diethyleneglycol dioleate or ethylene glycol distearate, or aliphatic acid estersof alkylene oxide sorbitans, such as polyethylene oxide sorbitanmonolaurate or polyethylene oxide sorbitan trioleate, are also suitable.Other suitable antifoams are phosphoric esters, such as tributylphosphate or triisobutyl phosphate, phthalates, such as dibutylphthalates, to siloxanes, such as polydiniethylsiloxane and itsderivatives, as obtained, for example, by hydrosilylation with allylalkoxylates. Anionic antifoams, such as the sulfuric monoesters ofethoxylated (alkyl)phenols, for example the sodium salt of methylpolypropylene oxide sulfate and the sodium salt of n-dodecylphenolethoxylate sulfate, or phosphates of ethoxylated fatty alcohols, such aspolyethylene oxide stearyl phosphate, are furthermore suitable. Suchantifoams are usually used in amounts of from 0.05 to 10, preferablyfrom 0.5 to 5, % by weight, based on the polymers.

[0314] The antifoams can be combined with the polymer in various ways.If the polymer is present, for example, in the form of an aqueoussolution, the antifoam can be added in solid or dissolved form to thepolymer solution. If the antifoam is insoluble in the aqueous polymersolution, emulsifiers or protective colloids may be added to stabilizeit.

[0315] If the novel components (A) and (B) are present in the form of asolid, as obtained, for example, from spray-drying or fluidized-bedgranulation, the antifoam can be admixed in the form of a solid or, inthe case of the spray-drying process or spray granulation process, canbe compounded together with the polymer.

[0316] Use as Biodegradable Polymers, for Example as Materials forImplants, Surgical Suture Materials and Garbage Bags

[0317] Regarding this use of the components (A) and (B) describedherein, reference may be made to EP-A 0 654 492, in particular to thesection extending from page 7, line 53 to page 11, line 39.

[0318] The novel components (A) and (B), in particular when aliphaticpolyesters are involved, can be used, for example, as biodegradablepolymers for implants, surgical suture material and garbage bags.

[0319] For use as garbage bags, the components under discussion here aremolded by a generally customary blow molding method to give sucharticles. If conventional packaging materials, such as packagingcontainers for foods, are to be produced, the novel components can alsobe prepared in the form of foams, conventional methods being employed inturn here.

[0320] If the novel components have fiber-forming properties, as is thecase, for example, with polyesters, they can be spun into fibers, whichthen in turn can be used, for example, for surgical suture materials,owing to their biodegradability.

[0321] They are used in the form of individual fibers or in the form offiber fabrics.

[0322] For fiber production, too, conventional methods are employed.

[0323] Use as Component in Water-Soluble Adhesives, for ExampleWallpaper Adhesives

[0324] In this use of the components (A) and (B), reference may be madeto EP-A 0 393 491 for further details. Thus, the present invention alsorelates to the use of the components (A) and/or (B) as redispersionpolymers in free-flowing fine-particle dry powders based on awater-soluble and/or water-swellable combination of these componentswith nonionic cellulose ethers, if necessary as a mixture with furtherassistants and/or without adhesive power.

[0325] The present invention also accordingly relates to free-flowingfine-particle dry powders based on a water-soluble and/orwater-swellable combination of nonionic cellulose ethers and driedredispersion polymers, if desired as a mixture with further assistantswith and/or without adhesive power. According to the invention, in thesefree-flowing fine-particle dry powders, the particle structure of the atleast predominant fraction of the particulate dry material has closedcores of the nonionic cellulose ethers which are surrounded by a shellof the redispersion polymer or firmly bonded thereto. In the respectiveindividual particle, in particular a majority of cores of nonioniccellulose ethers can be firmly enclosed by the polymer shell, it beingpossible for these individual cores based on the nonionic celluloseethers also to have different particle sizes. Nonionic cellulose ethersare understood by those skilled in the art as meaning alkyl, aralkyl andhydroxyalkyl ethers or cellulose. There are simple ethers having onlyone substituent and mixed ethers having two or more differentsubstituents in the cellulose chain. Thus, for example in the case ofmethylcellulose, the solubility and the flocculation point of thecellulose derivative can be influenced in a specific manner by anadditional, slight alkoxylation by reaction with ethylene oxide and/orpropylene oxide.

[0326] These free-flowing fine-particle dry powders are prepared bythorough mixing of the nonionic cellulose ethers in powder form or inthe form of an aqueous powder suspension with the aqueous polymerdispersion, it being possible, if desired, also to mix in additionalamounts of water.

[0327] Suitable nonionic cellulose ethers for the purposes of theinvention are all compounds of this type which in their dissolutionbehaviour exhibit the phenomenon of flocculation at elevatedtemperatures, preferably at temperatures or at least about 60° C., andare thus to be characterized by the turbidity or flocculation point. Ifnecessary. this property can be rapidly and easily determined by alaboratory experiment. Alkylcelluloses are particularly suitable here.The most important class comprises lower alkylcelluloses whose alkylradicals have in particular 1 to 3 carbon atoms. The member of thisclass which is widely used in practice is methylcellulose. The degree ofetherification of such nonionic cellulose ethers may be, for example, inthe range of from about 1.0 to 1.3 as the lower limit and up to 2.5 to3.0 as the upper limit, in particular in the range from 1.3 to 2.6. Thecellulose ethers, preferably methylcellulose, may additionally bealkoxylated, for example ethoxylated and/or propoxylated, and degrees ofalkoxylation of from about 0.05 to 1.5 may be preferred here.

[0328] Suitable polymer compounds redispersible in water are thereaction products (A) and/or polymers (B) described herein. Bothhomopolymers and/or copolymers of the classes of substances selected ineach case are suitable here. Typical members of these polymer compoundsare vinyl esters of lower carboxylic acids, vinyl acetate and/or vinylpropionate being particularly important. In addition to the ishomopolymers of this type, copolymers, for example vinyl acetate/maleatecopolymers or ethylene/vinyl acetate copolymers, are used in practice. Afurther important class comprises corresponding (meth)acrylate homo-and/or copolymers, an example of suitable copolymers being styreneacrylate.

[0329] These aqueous polymer dispersions comprising component (A) and/or(B) are now subjected to spray-drying not as such but rather—if desiredafter dilution with further amounts of water—after heating to atemperature level which corresponds at least to the turbidity orflocculation point of the nonionic cellulose ether or ethers to beincorporated. Temperatures which are slightly, for example from 10 to20° C., above the respective turbidity point can preferably be employed.

[0330] If such a slurry is kept permanently at, such a temperaturelevel, it is possible without problems to incorporate even large amountsof the nonionic alkylcellulose ethers as preformed dry powder into theliquid phase without thereby shifting the viscosity of the slurry intoregions which would make the use of the spray technology impossible.Under the conditions according to the invention, there is instead alimited increase in the slurry viscosity, for example in the range whichotherwise also occurs with addition of inert additives, for example withthe addition of alpha-cellulose powder having a similar particledistribution or other conventional fillers.

[0331] The mixing ratios of nonionic cellulose ether to redispersionpolymer, calculated in each case as a solid, may be varied within a widerange. In particular, corresponding mixing ratios of from about 5:95 to95:5 are suitable. Preferred mixing ratios of these two main componentsare roughly in the range from 60:40 to 40:60, good products beingobtained in the region of about identical ratios or with only a slightexcess, based on weight, of the nonionic cellulose ethers.

[0332] On spraying such a slurry, a free-flowing fine-particle dryproduct is obtained, which virtually exclusively comprisespolymer-coated nonionic alkylcellulose cores of a relatively uniformcomposition and particle structure. The mean particle size of the novelproducts, based on the initial grading curve of the cellulose ethersused, for example in the form of methylcellulose used, is substantiallyabove the mean particle size applicable to commercial redispersionpowders. It may be preferable to bring the novel free-flowing powders tomean particle diameters of from about 50 to 500 μm, preferably fromabout 100 to 300 μm.

[0333] Furthermore, the particles described above may undergo at leastpartial agglomeration, which results in agglomerates which consist of atleast two, formerly independent particles which may be joined to oneanother with different adhesive strengths.

[0334] In contrast to physical mixtures, the spray-dried productsobtained according to the invention do not give rise to any significantamounts of dust, which is to be regarded as a considerable advantage intheir processing.

[0335] According to a further feature of the invention, it is possibleto incorporate additional assistants with and/or without adhesiveproperties into the novel frees flowing fine-particle powders.

[0336] Examples of such assistants are wetting agents and preservatives,consistency-imparting substances and additional components havingadhesive power, such as natural starch, swellable starch, starch ethers,dextrins, ionic cellulose ethers and/or other aqueous polymerformulations.

[0337] These assistants present in addition to the main componentspreferably account for a constantly minor amount compared with the maincomponents comprising nonionic cellulose ether and redispersion polymer.

[0338] The spray-drying is effected in a manner known per se, usually inspray towers, and the slurry to be dried can be sprayed in with the aidof atomizing disks or airless or binary nozzles.

[0339] The field of use of the novel multicomponent powders covers theentire area for the use of such mixtures of substances. Examples are theuse as wall covering adhesives, in particular wallpaper adhesives, andthe use as an improving additive to coating materials, such as paintsand varnishes, and to cement-based systems. These powders areparticularly suitable as additives in filling and leveling compounds,tile adhesives and plaster-based filling compounds. Products spray-driedaccording to the invention constitute a raw material which permitsaccess to hitherto unachieved application benefits in the adhesives andbuilding chemicals sector, within wide ranges.

[0340] For further details regarding the type of the further componentsand the preparation of the dry powder described above, reference may bemade to EP-A 0 393 491.

[0341] Use as Adhesive for Floor Coverings

[0342] The present invention furthermore relates to the use ofcomponents (A) and (B) in the form of aqueous adhesive compositions, inparticular as adhesives for floor coverings. For this purpose, thecomponents (A) and/or (B) are mixed with polyurethane latices in amanner known per se, if required an inert filler, a plasticizer and acrosslinking agent also being part of the composition. The amount of thecomponents (A) and/or (B) varies within a range from 1 to 20% by weight.Further details regarding this application are given in U.S. Pat. No.5,455,293, whose disclosure in this context is hereby fully incorporatedin the context of the present application.

[0343] Use as Thickener of Aqueous or Predominantly Aqueous Systems

[0344] The novel components (A) and (B) are suitable for thickeningaqueous or predominantly aqueous systems, such as surface coatings,print pastes and pigment pastes, filler and pigment dispersions,textiles, leather and paper assistants, formulations for mineral oilproduction, formulations of detergents, adhesives, waxes for polishes,formulations for pharmaceutical and veterinary purposes, crop protectionformulations, cosmetic articles, etc. Water itself can also be thickenedwith the novel components (A) and (B) in order subsequently, ifrequired, to add further additives to said water or to add said wateritself to aqueous formulations. The novel thickeners can be used inmixtures with other thickeners, for example those based onpolyacrylates, cellulose derivatives or inorganic thickeners.

[0345] Examples of aqueous systems which can be thickened according tothe invention are aqueous polyacrylate dispersions, aqueous dispersionsof copolymers of olefinically unsaturated monomers, aqueous polyvinylacetate dispersions, aqueous polyurethane dispersions, aqueous polyesterdispersions and in particular ready-to-use formulations of the typediscussed above and based on such dispersions.

[0346] The novel components (A) and (B) can of course be used as such,preferably in the form of granules or, if required, powders. However,liquid formulations which, in addition to the novel polyurethanes,contain water, solvents, such as butyldiglycol, isopropanol,methoxypropyl acetate, ethylene glycol and/or propylene glycol, nonionicemulsifiers, surfactants and/or, if required, further additives arepreferably used since this substantially facilitates the incorporationof the novel thickeners into aqueous or predominantly aqueous systems.

[0347] The ready-to-use formulations of the novel components (A) and (B)are particularly preferably aqueous solutions or dispersions having asolids content of from 10 to 80, preferably from 30 to 60, particularlypreferably from 40 to 50, % by weight.

[0348] The amount of the novel components (A) and (B) which are added tothe aqueous or predominantly aqueous systems for achieving the desiredthickening depends on the respective intended use and can be determinedby those skilled in the art in a few experiments. As a rule, from 0.05to 10, preferably from 0.1 to 4, particularly preferably from 0.1 to 1,% by weight of the novel components (A) and (B) are used, thesepercentages being based on the solids content of the components (A) and(B) on the one hand and on the solids content of the aqueous system tobe thickened, on the other hand.

[0349] Use as Component in Pressure-Sensitive Adhesive Materials

[0350] The components (A) and (B) described herein can also be used ascomponents in pressure-sensitive adhesive materials. Such components (A)and/or (B) based on block copolymers containing polymer blocks formedfrom vinylaromatics (A blocks), preferably styrene, and those formed bypolymerization of 1,3-dienes (D blocks), preferably butadiene andisoprene, are preferably employed.

[0351] According to the invention, both homopolymer and copolymer blockscan be used. The resulting block copolymers may contain identical ordifferent D blocks, some or all of which can be completely hydrogenatedor which can be selectively hydrogenated. Block copolymers may have alinear A-D-A structure. Block copolymers having a radial structure andstar and linear multiblock copolymers may also be used. A-D two-blockcopolymers may be present as further components. Block copolymers may bemodified, for example functionalized by reaction with maleic anhydride.According to the invention, block copolymers of vinylaromatics andisobutylene can also be used. All of the abovementioned polymers can beused alone or in mixture with one another. Typical concentrations inwhich the styrene block copolymers are used are from 15 to 75,preferably from 30 to 60, particularly preferably from 35 to 55, % byweight.

[0352] Suitable tackifiers include: colophony and its derivatives,aliphatic, aromatically modified aliphatic, aromatic and phenol-modifiedadhesive resins, to mention but a few. The concentrations in which theresins are used are typically from 15 to 75, preferably from 30 to 65,particularly preferably from 35 to 60, % by weight. Where colophony andits derivatives are used, esters of partially and completelyhydrogenated colophony are preferably employed.

[0353] Homopolymers and copolymers of vinylaromatics, for examplestyrene or α-methylstyrene, polyphenylene oxides and also phenyleneoxide-modified resins may be used as resins compatible with the terminalblocks, chiefly resins compatible with the vinylaromatic blocks.

[0354] Further optimum components of the mixture comprise plasticizeroils and liquid resins (concentration of use from 0 to not more thanabout 35% by weight), fillers (reinforcing and nonreinforcing), forexample silica, in particular synthetic silica, glass (milled or in theform of beads), aluminas, zinc oxides, calcium carbonates, titaniumdioxide, carbon blacks, to mention but a few, and antiaging compositions(primary and secondary antioxidants, light stabilizers, antiozonants,metal deactivators, etc.). Components of the mixture also comprisepolymers which in particular affect the ozone resistance of the blockcopolymers, for example polyvinyl acetates and ethylene/vinyl acetatecopolymers.

[0355] Further polymers which may be used are natural and syntheticpolymers, for example natural rubber, synthetic polyisoprenes,polybutadienes, polychloroprenes. SBR, Kraton Liquid (Shell Chemicals),low molecular weight styrene/diene block copolymers, for example KratonLVSI 101, polyisobutylene, etc., which may replace up to about 50% byweight of the vinylaromatic-containing block copolymers.

[0356] Novel pressure-sensitive adhesive materials may have beenchemically crosslinked, in particular radiation-crosslinked (for exampleby UV irradiation, γ-irradiation or irradiation by means of fastelectrons).

[0357] Novel adhesive materials are optionally those whose tack isproduced only as a result of thermal activation.

[0358] Suitable pressure-sensitive adhesive materials in addition tothose described above and based on vinylaromatic-containing blockcopolymers are all those which have tensile strength and cohesionsufficient for the release process. Corresponding pressure-sensitiveadhesive materials can be used alone or in combination with those basedon vinylaromatic-containing block copolymers. For example, tackyacrylate copolymers copolymerized with macromonomers are suitableaccording to the invention, the macromonomers having a glass transitiontemperature of >+40° C. The high tensile strength of correspondingcopolymers is probably achieved by the association of the macromonomers.Suitable macromonomers are, for example, methacryloyl-terminatedpolymethyl methacrylates,

[0359] The pressure-sensitive adhesive materials described above can beused for self-adhesive tapes for tamper-proof applications, the fixingof posters, pictures, calendars, postcards, information signs,self-adhesive hooks and labels, for example price labels, and for theadhesive bonding of foam.

[0360] Regarding this use, reference may be made to DE-A 196 49 728,whose relevant content on pages 3 and 4 is hereby fully incorporated byreference in the context of the present application.

[0361] Use as Solid or Liquid Adhesive

[0362] According to the present inventor, the components (A) and (B) canalso be used in solid adhesives in order to impart to them the adhesionwhich they produce. Particularly used components (A) and (B) are thosewhich may be selected from the group consisting of polyvinyl acetatehomopolymers, polyvinyl acetate copolymers, partially or completelyhydrolyzed polyvinyl alcohol, polyvinyl butyral, polyvinylpyrrolidone,polyacrylic acid salts, polymethacrylic acid salts, polyacrylate,polymethacrylate, various gums, polysaccharides and rubber. Thecomponents (A) and/or (B) may be a mixture of more than one of thesechemicals. Preferably, the components (A) and/or (B) are a mixture ofpolyvinyl alcohol and polyvinylpyrrolidone. It has been found that atleast about 15%, preferably at least 20%, of the components (A) and/or(B) in the solid adhesive result in good adhesion by the solid adhesive.Too large an amount of the components (A) and/or (B) cannot be dissolvedin water. The components (A) and/or (B) are therefore preferably limitedto from about 15 to 42%, better still from about 20 to 36%, in the solidadhesive.

[0363] Benzylidenesorbitol is present in this solid adhesive in order toserve as a gelatinizing composition or gel former. Chemicals which maybe used as benzylidenesorbitol are those which are used as abenzylidenesorbitol in the references. Among these chemicals,dibenzylidene (penta- or hexahydro-)saccharide is preferred,dibenzylidenesorbitol being particularly preferred. At least about 0.3%,better still at least 0.8%, of benzylidenesorbitol should be present inthe solid adhesive in order to ensure appropriate strength properties ofa stick-like product produced from this solid adhesive. Too muchbenzylidenesorbitol cannot be dissolved in organic solvents. Thebenzylidenesorbitol in the solid adhesive is therefore preferablylimited to from about 0.3 to 6%, better still from about 0.8 to 4%.

[0364] At least about 25%, better still at least about 28%, of water ispresent in the solid adhesive in order to facilitate the dissolution ofthe benzylidenesorbitol. Too much water in the solid adhesive presentsdissolution of the benzylidenesorbitol and adversely affects theadhesion of the solid adhesive. Accordingly, the amount of water islimited to from about 25 to 60%, preferably from about 28 to 57%, in thesolid adhesive.

[0365] Since this solid adhesive contains a large amount of water, it ispossible for various microorganisms to multiply in the solid adhesiveduring prolonged storage and release. The growth of variousmicroorganisms adversely affects the properties of the solid adhesive.To prevent the growth of various microorganisms in the solid adhesive,the latter contains at least 0.001%, preferably 0.003%, better still atleast 0.005%, of a preservative, for example an isothiazolinepreservative. Too high a content of isothiazoline preservativesadversely affects the physical properties of the solid adhesive andresults in higher costs of the solid adhesive. Accordingly, theisothiazoline preservatives are limited to from about 0.001 to 0.5%,preferably from about 0.003 to 0.1%, better still from about 0.005 to0.05%, in the solid adhesive. The isothiazoline preservatives can beselected from the group consisting of 1,2-benzisothiazolin-3-one,methylisothiazoline, octylisothiazoline and isothiazolinone.Isothiazoline preservatives may be a mixture of more than one of thesechemicals. Among these chemicals, 1,2-benzisothiazolin-3-one ispreferred.

[0366] At least about 12% and preferably at least 13% of organic solventis present in the solid adhesive in order to facilitate the dissolutionof benzylidenesorbitol. Too high a content of solvent adversely affectsthe adhesive and strength properties of a stick-like product producedfrom solid adhesive. Accordingly, the organic solvents are preferablylimited to from about 12 to 50%, better still from about 13 to 43%.Suitable organic solvents are water-miscible organic solvents,preferably polar organic solvents. The organic solvents can be selectedin particular from the group consisting of various alcohols, glycolalkyl ethers, alkyl ethers and pyrrolidone derivatives. In particular,the organic solvent can be selected from the group consisting of3-methoxy-3-methyl-1-butanol, N-methyl-2-pyrrolidone, 2-butoxyethanol,isopropyl alcohol, 1-ethoxy-2-propanol, 1-methoxy-2-propanol and2-ethoxyethanol. The organic solvent may be a mixture of more than oneof these chemicals. Among these, glycol (of 2 to 6 carbon atoms) alkyl(of 1 to 3 carbon atoms) monoether is particularly preferred.

[0367] Further chemicals may be present in this solid adhesive. Forexample, from 0.1 to 1%, preferably from about 0.3 to 0.7%, of antirustcompositions may be present in the solid adhesive on shaping of saidadhesive and when said adhesive is shaped into a stick-like product, inorder to prevent the formation of rust on metallic parts. Preferably,benzotriazole corrosion inhibitor is present in the solid adhesive. Inaddition, fragrances and/or pigments may be present in the solidadhesive.

[0368] Solid adhesives in the context of the present text are all typesof adhesives which are present in the solid state at ambienttemperature, for example at room temperature. These include inparticular hotmelt adhesives, hotmelt pressure sensitive adhesives andpressure-sensitive adhesives. Said adhesives can also be applied, forexample, to substrate materials, for example to tape-like substratematerials, as used in the production of adhesive tapes.

[0369] Regarding further details, reference may be made to DE-A 197 55683.

[0370] Use for Producing Self-Cleaning Surfaces of Articles (LotusEffect)

[0371] The novel components (A) and (B), in particular the novel blockcopolymers, are extremely useful for producing self-cleaning surfaces ofarticles, as described, for example, in WO 96/04123, the relevantcontent of which is hereby fully incorporated by reference in thecontext of the present application. Particularly advantageous blockcopolymers are those which, owing to the incompatibility of theirrespective blocks form self-cleaning (i.e. hydrophobic andcorrespondingly structured) surfaces by self-organization afterapplication.

[0372] Use as Stain Inhibitors in Solid and Liquid Formulations

[0373] The novel components (A) and (B) can also be used as staininhibitors in solid and liquid formulations. In this application, theyare used in particular in detergents.

[0374] In this respect, reference may be made to the publication inResearch Disclosure of August 1998, page 1047 et seq., the relevantcontent of which is hereby fully incorporated by reference in thecontext of the present application.

We claim:
 1. The use of reaction product (A) which can be prepared bymeans of a process comprising the following stage (i): (i) Reaction,wider free radical conditions, of a reaction mixture comprising at leastone monomer (a), capable of free radical reaction, in the presence of atleast one radical of the formula (III)

where R¹ to R³, in each case independently of one another, are hydrogen,methyl or a radical-stabilizing and/or bulky group selected from anunsubstituted or substituted, linear or branched alkyl of two or morecarbon atoms, cycloalkyl, alcohol, ether, polyether, amine, aralkylradical, a substituted or unsubstituted aromatic, heterocyclic orolefinic hydrocarbon, a halogen atom, a substituted or unsubstituted,linear or branched alkenyl or alkynyl group, —C(O)R₅, —C(O)OR₅,—CR₅R₆—O—R₇, —O—C(O)R₅, —CN, —O—CN, —S—CN, —O—C═NR₅, —S—C═NR₅,—O—CR₅R₆—CR₇R₈NR₉R₁₀, —N═C═O, —C═NR₅, —CR₅R₆-Hal, —C(S)R₅,—CR₅R₆—P(O)R₇R₈, —CR₅R₆—PR₇R₈, —CR₅R₆—NR₇R₈, —CR₅R₆(OR₇)(OR₈),—CR₅R₆(OR₇)(NR₈), —CR₅R₆(NR₇)(NR₈), an anhydride, acetal or ketal group,—SO₂R₅, an amidine group, —NR₅C(S)NR₆, —NR₅C(S)—OR₆, —N═C═S, —NO₂,—C═N—OH, —N(R₅)═NR₆, —PR₅R₆R₇, —OSiR₅R₅R₇ or —SiR₅R₆R₇, where R₅ to R₁₀,independently of one another in each case, are defined in the same wayas R₁ to R₄, or two of the radicals R₁ to R₄ form a C₄- to C₇-ring whichin turn may be substituted or unsubstituted and, if required, maycontain one or more heteroatom, with the proviso that at least two ofthe radicals R₁ to R₃ are a radical-stabilizing and/or bulky group asdefined above, as a component in coating materials, in particular infinishes and coating materials, as a component in toners, as a componentin cosmetics, as a component in resin material, as a component inretention aids for papermaking, as a component in solubilizers inpharmaceutical and cosmetic formulations, as incrustation inhibitorsand/or soil-release polymers in detergents, as filtration assistants andfor protecting and clarifying beverages, as a component indisinfectants, as a component in elastomeric binders in printing plates,as a dispersant, preferably in inkjet pigment formulations, as anassistant in a tablet matrix, as an assistant in the plasticizing ofconcrete, as biodegradable polymers for, for example, materials forimplants, surgical suture materials and garbage bags, as a component inwater-soluble adhesives, as adhesives for floor coverings, as thickenersof aqueous or predominantly aqueous systems, as a component in sheets,moldings, foams and fibers, as a component in pressure-sensitiveadhesive materials, as a component in solid or liquid adhesives, forproducing self-cleaning surfaces of articles, as stain inhibitors insolid and liquid formulations, as a component of plastics used inautomotive construction, in the household sector, for leisure articles,in the production of road signs, window profiles, lamp covers, gardenfurniture, boats, surfboards, toys, in the packaging sector, in theproduction of massage apparatuses and housings therefor, in theproduction of medical equipment, in the production of equipment forinformation processing and transmission, in the production of extensivewall elements, in transport containers, in housings for electricalequipment, in moldings for the construction sector or in grating covers.2. The use of a polymer (B) which can be prepared by a processcomprising the stage (ii): (ii) Reaction of the reaction product (A)obtained in stage (i), under free radical conditions, in the presence ofat least one monomer (b) capable of free radical homopolymerization orcopolymerization, as a component in coating materials, in particular infinishes and coating materials, as a component in toners, as a componentin cosmetics, as a component in resin material, as a component inretention aids for papermaking, as a component in solubilizers inpharmaceutical and cosmetic formulations, as incrustation inhibitorsand/or soil-release polymers in detergents, as filtration assistants andfor protecting and clarifying beverages, as a component indisinfectants, as an elastomeric binder in printing plates, as adispersant, preferably in inkjet pigment formulations, as an assistantin a tablet matrix, as an assistant in the plasticizing of concrete, asbiodegradable polymers for, for example, materials for implants,surgical suture materials and garbage bags, as a component inwater-soluble adhesives, as adhesives for floor coverings, as thickenersof aqueous or predominantly aqueous systems, is as a component inpressure-sensitive adhesive materials, as a solid or liquid adhesive,for producing self-cleaning surfaces of articles, as stain inhibitors insolid and liquid formulations, as a component of plastics used inautomotive construction, in the household sector, for leisure articles,in the production of road signs, window profiles, lamp covers, gardenfurniture, boats, surfboards, toys, in the packaging sector, in theproduction of massage apparatuses and housings therefor, in theproduction of medical equipment, in the production of equipment forinformation processing and transmission, in the production of extensivewall elements, in transport containers, in housings for electricalequipment, in moldings for the construction sector or in grating covers.3. The use as claimed in claim 1, wherein the radical of the formula(III) is derived from at least one compound of the formula (I)

where R₁ to R₄, in each case independently of one another, are hydrogen,methyl or a radical-stabilizing and/or bulky group selected from anunsubstituted or substituted, linear or branched alkyl of two or morecarbon atoms, cycloalkyl, alcohol, ether, polyether, amine, aralkylradical, a substituted or unsubstituted aromatic, heterocyclic orolefinic hydrocarbon, a halogen atom, a substituted or unsubstituted,linear or branched alkenyl or alkynyl group, —C(O)R₅, —C(O)OR₅,—CR₅R₆—O—R₇, —O—C(O)R₅, —CN, —O—CN, —S—CN, —O—C═NR₅, —S—C═NR₅,—O—CR₅R₆—CR₇R₈NR₉R₁₀, —N═C═O, —C═NR₅, —CR₅R₆-Hal, —C(S)R₅,—CR₅R₆—P(O)R₇R₈, —CR₅R₆—PR₇R₈, —CR₅R₆—NR₇R₈, —CR₅R₆(OR₇)(OR₈),—CR₅R₆(OR₇)(NR₈), —CR₅R₆(NR₇)(NR₈), an anhydride, acetal or ketal group,—SO₂R₅, an amidine group, —NR₅C(S)NR₆, —NR₅C(S)—OR₆, —N═C═S, —NO₂,—C═N—OH, —N(R₅)═NR₆, —PR₅R₆R₇, —OSiR₅R₆R₇ or —SiR₅R₆R₇, where R₅ to R₁₀,independently of one another in each case, are defined in the same wayas R₁ to R₄, or two of the radicals R₁ to R₄ form a C₄- to C₇-ring,which in turn may be substituted or unsubstituted and may contain one ormore heteroatoms, with the proviso that at least two of the radicals R₁to R₄ are a radical-stabilizing and/or bulky group, as defined above, orthe compounds are diphenylethylene, dinaphthylethylene,4,4′-vinylidenebis N,N′-dimethylaniline),4,4′-vinylidenebis(aminobenzene) or cis- and trans-stilbene.
 4. The useas claimed in claim l, wherein the radical of the formula (III) isderived from at least one compound of the formula (II):

where R₁ to R₄ and R₁₁ and R₁₂, in each case independently of oneanother, are hydrogen, methyl or a radical-stabilizing and/or bulkygroup selected from an unsubstituted or substituted, linear or branchedalkyl of two or more carbon atoms, cycloalkyl, alcohol, ether,polyether, amine aralkyl radical, a substituted or unsubstitutedaromatic, heterocyclic or olefinic hydrocarbon, a halogen atom, asubstituted or unsubstituted, linear or branched alkenyl or alkynylgroup, —C(O)R₅, —C(O)OR₅, —CR₅R₆—O—R₇, —O—C(O)R₅, —CN, —O—CN, —S—CN,—O—C═NR₅, —S—C═NR₅, —O—CR₅R₆—CR₇R₈NR₉R₁₀, —N═C═O, —C═NR₆, —CR₅R₆-Hal,—C(S)R₅, —CR₅R₆—P(O)R₇R₈, —CR₅R₆—PR₇R₈, —CR₅R₆—NR₇R₈, —CR₅R₆(OR₇)(OR₈),—CR₅R₆(OR₇)(NR₈), —CR₅R₆(NR₇)(NR₈), an anhydride, acetal or ketal group,—SO₂R₅, an amidine group, —NR₅C(S)NR₆, —NR₅C(S)—OR₆, —N═C═S, —NO₂,—C═N—OH, —N(R₅)═NR₆, —PR₅R₆R₇, —OSiR₅R₆R₇ or —SiR₅R₆R₇, where R₅ to R₁₀,independently of one another in each case, are defined in the same wayas R₁ to R₄, or two of the radicals R₁ to R₄ form a C₄- to C₇-ring whichin turn may be substituted or unsubstituted and, if required, maycontain one or more heteroatoms, with the proviso that at least two ofthe radicals R₁ to R₄ are a radical-stabilizing and/or bulky group, asdefined above.
 5. The use as claimed in any of the preceding claims, theradical of the formula (III) comprising the following combinations asradical-stabilizing and/or bulky groups: at least one substituted orunsubstituted phenyl and —C(O)R₅; at least one substituted orunsubstituted phenyl and —CN; at least one substituted or unsubstitutedphenyl and —C(O)OR₅; independently of one another, at least twosubstituted or unsubstituted phenyl groups; independently of oneanother, at least two —C(O)R₅; and independently of one another, atleast two —CN.
 6. The use as claimed in any of the preceding claims, theradical (III) being derived from the following compounds of the formula(I) or (II) or mixtures of two or more thereof:1,1,4,4-tetraphenyl-1,3-butadiene 1,4-bis(2-methylstyryl)benzene1,2,3,4,5-pentaphenyl-1,3 -cyclopentadiene1,2,3,4-tetraphenyl-1,3-cyclopentadiene acenaphthylene cis- andtrans-alpha-methylstilbene cis- and trans-4,4′-diphenylstilbene,diphenylethylene, dinaphthylethylene,4,4′-vinylidenebis(N,N′-dimethylaniline),4,4′-vinylidenebis(amino-benzene), cis- and trans-stilbene, trans-trans-and trans-cis- and cis-cis-1,4-diphenyl-1,3-butadienealpha,omega-tetraphenylpolyethyne diphenylfulvene triphenylethenetetraphenylethene 1-cyano-1-phenylethylene;1-alkoxycarbonyl-1-phenylethylene; 1,1-dialkoxycarbonyl-2-ethylethylene;1,1-dialkoxycarbonyl-2-phenylethylene, 1,1-dialkoxycarbonyl-2,2-dimethylethylene;1,1-dialkoxycarbonylmethylethylene; 9-methylenexanthene;9-methylenethioxanthene, 9-methylene-10-H-acridine, diphenylethylene,dinaphthylethylene, 4,4′-vinylidenebis(N,N′-dimethylaniline),4,4′-vinylidenebis(aminobenzene), cis- and trans-stilbene,1,2-bis(trimethylsilyloxy)tetraphenylethane (TPSE),diethyl-2,3-dicyano-2,3-di(p-tolyl)succinate, hexaphenylethane,compounds of the structure (Ph₂CR₁—CR₁(Ph)₂, where Ph is substituted orunsubstituted phenyl and R₁ is selected from the group consisting of:hydrogen, ethyl, —C₂H₄—, —OC₆H₅, OSi(CH₃)₃, —OH, —OC(O)CH₃, —OCH₃, —CH₃,—CO₂C₂H₅, —CN; —OC(O)CH═CH₂, 1,1,2,2-tetraphenyl-1,2-diphenoxyethane(TPPA); 1,1,2,2-tetraphenyl-1,2-bis(trimethylsilyloxy)ethane (TPSA) and1,2,2,2-tetraphenyl-1,2-dicyanoethane (TPCA);1,2-diphenyl-1,2-dicyano-1,2-dimethylethane.
 7. The use as claimed inany of claims 1 to 6, the low molecular weight base being NaOH, KOH,ammonia, diethanolamine, triethanolamine, mono-, di- or triethylamine,dimethylethanolamine or a mixture of two or more thereof.